Polymers derived from norbornadiene and maleic anhydride and use thereof

ABSTRACT

Embodiments encompassing a series of compositions containing polymers of norbornadiene and maleic anhydride monomers which are useful in forming a variety of photopatternable structures are disclosed and claimed. The compositions are useful as permanent dielectric materials. More specifically, embodiments encompassing compositions containing a series of ter- and tetrapolymers of a variety of norbornadiene, maleic anhydride, maleimide and norbornene-type cycloolefinic monomers in which maleic anhydride is fully or partially hydrolyzed (i.e., ring opened and fully or partially esterified), and a photoactive compound are disclosed, which are useful in forming permanent dielectric materials having utility in a variety of electronic material applications, among various other uses.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/273,553, filed Dec. 31, 2015, which is incorporated herein byreference in its entirety.

TECHNICAL FIELD

The present invention relates to compositions containing a series ofpolymers derived from a variety of polycycloolefinic monomers, maleicanhydride and maleimide monomers, which are useful as permanentdielectric materials. More specifically, the present invention relatesto compositions containing a series of ter- and tetrapolymers of avariety of norbornadiene, norbornene-type cycloolefinic monomers,maleimide monomers and maleic anhydride in which maleic anhydride isfully or partially hydrolyzed (i.e., ring opened and fully or partiallyesterified), which are useful in forming permanent dielectric materialshaving utility in a variety of electronic material applications, amongvarious other uses.

BACKGROUND

As the microelectronic devices are fabricated in smaller geometriesthere is an increasing demand for advanced materials that meet thestringent requirements of confined smaller geometries. In particular,sub-micron device geometries have become common place in the fabricationof a variety of microelectronics packages for memory and logicintegrated circuits (ICs), liquid crystal displays (LCDs), organic lightemitting diodes (OLEDs) and other radio frequency (Rf) and microwavedevices. For example, devices such as radio frequency integratedcircuits (RFICs), micro-machine integrated circuits (MMICs), switches,couplers, phase shifters, surface acoustic wave (SAW) filters and SAWduplexers, have recently been fabricated with submicron dimensions.

With such smaller geometries comes a requirement for dielectricmaterials with low dielectric constants to reduce or eliminate anycross-talk between adjacent signal lines or between a signal line and adevice feature (e.g. a pixel electrode) due to capacitive coupling.Although many low dielectric (low-K) materials are available formicroelectronic devices, for optoelectronic devices such materials mustalso be broadly transparent in the visible light spectrum, not requirehigh temperature processing (greater than 300° C.) that would beincompatible with other elements of such an optoelectronic device, andbe both low-cost and feasible for large scale optoelectronic devicefabrication.

In addition, many of such applications require that such materialsfeature good thermomechanical properties, including low wafer stress (30MPa or less), high elongation to break (ETB), high tensile stress, highglass transition temperature (T_(g)), high thermal decompositiontemperature (higher than 300° C.), among others. It should be noted thata few of the currently used polyimide polymers do not meet many of theseproperties, for example, they generally exhibit wafer stress higher than30 MPa. Furthermore, there is an heightened interest in developingenvironmentally friendly aqueous developable materials thus avoiding theuse of organic solvents which results in unwanted organic waste.

Thus, it would be desirable to have a material capable of forming aself-imagable layer, which exhibits improved thermomechanicalproperties. Such material should also be easy to apply to a substrate,have a low dielectric constant (3.9 or less) and thermal stability totemperatures in excess of 300° C. Of course, it is also desirable tohave such materials available at a lower cost and feature suchproperties as positive photoimaging capability, aqueous base developingcapability, high transparency after heat stress and low weight loss atcuring temperatures. It has been reported that acrylic polymers, whichare inexpensive, offer good photoimaging properties and are aqueous basedevelopable, see for example, Japanese Patent Application Laid-open No.Hei 5-165214 and the radiation-sensitive resin composition comprising analicyclic olefin resin disclosed in Japanese Patent ApplicationLaid-open No. 2003-162054. Similarly, polyimides have been reported toprovide good thermal stability. However, these materials have certaindeficiencies and thus making them not so suitable for the applicationscontemplated herein. For instance, acrylics are not suitable forapplications requiring high thermal stability (i.e., temperatures higherthan 200° C.), and many of the polyimides in general are not suitablefor either positive tone or negative tone formulations requiring aqueousbase developability and generally do not exhibit desirable transparency,thus making them unsuitable in certain optoelectronic applications.Although some polyimides and polybenzoxazoles have low dielectricconstants but still may not have low enough permittivity to be effectivein highly integrated and/or miniaturized devices having increased wiringdensity and high signal speed. Furthermore, both polyimides andpolybenzoxazoles require cure temperatures in excess of 300° C., thusrendering them unsuitable for many applications. One such knownpolyimide material is the positive tone photosensitive resin comprisinga polyimide precursor and a diazoquinone-type compound disclosed inJapanese Patent No. 3,262,108.

Recently, it has been reported that certain copolymers containingnorbornene-type repeat units having pendent maleimide groups and maleicanhydride-type repeat units are useful in certain microelectronicapplications featuring self-image forming layer capability, whenimage-wise-exposed to actinic radiation, see co-pending U.S. PatentApplication Publication No. US-2014-0087293 A1.

However, there is still a need for cost effective permanent dielectricmaterials having not only self photopatternable properties but alsoexhibiting good properties, including improved thermomechanicalproperties, high resolution, retaining film thickness from the unexposedregions of a positive tone formulation (i.e., low dark field loss), lowthermal reflow after cure, improved stability to various chemicals andprocess conditions involved in the downstream process fabrication steps,such as, for example, in a device containing a redistribution layer(RDL), and/or solvent stripper operations, among others.

Thus it is an object of this invention to provide organic polymermaterials having aforementioned properties for a variety of electronicand/or optoelectronic device fabrication applications.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following accompanying figures and/or images.Where drawings are provided, it will be drawings which are simplifiedportions of a device provided for illustrative purposes only.

FIG. 1 shows FT-IR spectrum of two comparative composition embodimentsof this invention as further discussed herein.

FIG. 2 shows thermal properties of two specific composition embodimentsof this invention which are compared with two comparative compositionsas described herein.

FIG. 3 shows two dimensional top down image generated by a lasermicroscope of a positive tone lithographic image of 8, 9 and 10 μmisolated trenches at an exposure dose of 327 mJ/cm² of one of thephotosensitive composition embodiments of this invention.

FIG. 4 shows three dimensional image generated by a laser microscope ofa positive tone lithographic image of 15 μm square shaped via arrayobtained using one of the photosensitive composition embodiments of thisinvention.

FIG. 5 shows optical micrograph of a positive tone lithographic imagesof line and space pattern obtained from a photosensitive compositionembodiment of this invention.

DETAILED DESCRIPTION

Embodiments in accordance with the present invention are directed tovarious polymers, including but not limited to, polymers that encompassat least one repeating unit derived from a certain type of norbornadienemonomer as described herein, at least one second repeating unit derivedfrom a maleic anhydride-type monomer, as such are defined hereinafterand at least one third repeating unit derived from a maleimide, and tocompositions encompassing such polymers. Such polymer compositions beingcapable of forming self-imagable films useful as layers in themanufacture of microelectronic and optoelectronic devices. That is tosay that, after image-wise exposure to actinic radiation, such layers(or films) can be developed to form patterned layers (or films), wheresuch pattern is reflective of the image through which the layers (orfilms) was exposed. In this manner, structures can be provided that are,or are to become, a part of such microelectronic and/or optoelectronicdevices.

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the symbol “

” denotes a position at which the bonding takes place with anotherrepeat unit or another atom or molecule or group or moiety asappropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a radical of a group thatcontains carbon and hydrogen atoms, non-limiting examples being alkyl,cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term“halohydrocarbyl” refers to a hydrocarbyl group where at least onehydrogen has been replaced by a halogen. The term perhalocarbyl refersto a hydrocarbyl group where all hydrogens have been replaced by ahalogen.

As used herein, the expression “(C₁-C₁₅)alkyl” includes methyl and ethylgroups, and straight-chained or branched propyl, butyl, pentyl, hexyl,heptyl, and various other homolog groups. Particular alkyl groups aremethyl, ethyl, n-propyl, isopropyl and tert-butyl, etc. Derivedexpressions, such as “(C₁-C₁₅)alkoxy”, “(C₁-C₁₅)thioalkyl”“(C₁-C₁₅)alkoxy(C₁-C₁₅)alkyl”, “hydroxy(C₁-C₁₅)alkyl”,“(C₁-C₁₅)alkylcarbonyl”, “(C₁-C₁₅)alkoxycarbonyl(C₁-C₁₅)alkyl”,“(C₁-C₁₅)alkoxycarbonyl”, “amino(C₁-C₁₅)alkyl”, “(C₁-C₁₅)alkylamino”,“(C₁-C₁₅)alkylcarbamoyl(C₁-C₁₅)alkyl”,“(C₁-C₁₅)dialkylcarbamoyl(C₁-C₁₅)alkyl” “mono- ordi-(C₁-C₁₅)alkylamino(C₁-C₁₅)alkyl”, “amino(C₁-C₁₅)alkylcarbonyl”“diphenyl(C₁-C₁₅)alkyl”, “phenyl(C₁-C₁₅)alkyl”,“phenylcarboyl(C₁-C₁₅)alkyl” and “phenoxy(C₁-C₁₅)alkyl” are to beconstrued accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic radicals. Representative examples of “cycloalkyl” includeswithout any limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “(C₂-C₆)alkenyl” includes ethenyl andstraight-chained or branched propenyl, butenyl, pentenyl and hexenylgroups. Similarly, the expression “(C₂-C₆)alkynyl” includes ethynyl andpropynyl, and straight-chained or branched butynyl, pentynyl and hexynylgroups.

As used herein the expression “(C₁-C₄)acyl” shall have the same meaningas “(C₁-C₄)alkanoyl”, which can also be represented structurally as“R—CO—,” where R is a (C₁-C₃)alkyl as defined herein. Additionally,“(C₁-C₃)alkylcarbonyl” shall mean same as (C₁-C₄)acyl. Specifically,“(C₁-C₄)acyl” shall mean formyl, acetyl or ethanoyl, propanoyl,n-butanoyl, etc. Derived expressions such as “(C₁-C₄)acyloxy” and“(C₁-C₄)acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “(C₁-C₁₅)perfluoroalkyl” means that allof the hydrogen atoms in said alkyl group are replaced with fluorineatoms. Illustrative examples include trifluoromethyl andpentafluoroethyl, and straight-chained or branched heptafluoropropyl,nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups.Derived expression, “(C₁-C₁₅)perfluoroalkoxy”, is to be construedaccordingly.

As used herein, the expression “(C₆-C₁₀)aryl” means substituted orunsubstituted phenyl or naphthyl. Specific examples of substitutedphenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl,1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or“substituted naphthyl” also include any of the possible substituents asfurther defined herein or one known in the art. Derived expression,“(C₆-C₁₀)arylsulfonyl,” is to be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl(C₁-C₄)alkyl” means that the(C₆-C₁₀)aryl as defined herein is further attached to (C₁-C₄)alkyl asdefined herein. Representative examples include benzyl, phenylethyl,2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

As used herein, the expression “heterocycle” includes all of the knownreduced heteroatom containing cyclic radicals. Representative 5-memberedheterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl,pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl,and the like. Representative 6-membered heterocycle radicals includepiperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like.Various other heterocycle radicals include, without limitation,aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, andtriazocanyl, and the like.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl, (C₁-C₆)perfluoroalkoxy, —NH₂, Cl, Br,I, F, —NH(C₁-C₆)alkyl, and —N((C₁-C₆)alkyl)₂. However, any of the othersuitable substituents known to one skilled in the art can also be usedin these embodiments.

The statements below, wherein, for example, R₅ and R₆ are said to beindependently selected from a group of substituents, means that R₅ andR₆ are independently selected, but also that where an R₅ variable occursmore than once in a molecule, those occurrences are independentlyselected (e.g., if R₁ and R₂ are each contains a group of formula (A),R₅ can be hydrogen in R₁, and R₅ can be methyl in R₂). Those skilled inthe art will recognize that the size and nature of the substituent(s)can affect the number and nature of other substituents that can bepresent.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

As used herein, the terms “polymer composition,” or “terpolymercomposition” are used herein interchangeably and are meant to include atleast one synthesized polymer or terpolymer, as well as residues frominitiators, solvents or other elements attendant to the synthesis ofsuch polymers, where such residues are understood as not beingcovalently incorporated thereto. Such residues and other elementsconsidered as part of the “polymer” or “polymer composition” aretypically mixed or co-mingled with the polymer such that they tend toremain therewith when it is transferred between vessels or betweensolvent or dispersion media. A polymer composition can also includematerials added after synthesis of the polymer to provide or modifyspecific properties of such composition. Such materials include, but arenot limited to solvent(s), antioxidant(s), photoinitiator(s),sensitizers and other materials as will be discussed more fully below.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, e.g., polycyclic norbornadiene ornorbornene-type monomers, in accordance with formula (I) or (IV) andmaleic monomers of formula (II) or (III), wherein the resulting polymersare formed by 2,3 enchainment of norbornene-type monomers or 3,5enchainment of norbornadiene monomers with maleic anhydride or maleimidemonomers in an alternating fashion as shown below:

Where X is O or NR₁₀ where R₁₀ is as defined herein.

It should be understood that depending upon the monomeric compositionsin a given polymer the repeat units may not always be alternating. Thatis to say, for example, in a polymer containing other than 50:50 molarratios of combined norbornene-type monomers and norbornadiene monomerswith combined molar amounts of maleic anhydride and maleimide monomers,the repeat units are not always alternating but with random blocks ofmonomers with the higher molar content. It is also possible that certainmaleimide monomers may not alternate with norbornadiene or norbornenemonomers and may form random blocks. In addition, some norbornadienemonomers may polymerize in 2,3 enchainment fashion similar to norbornenemonomers and leaving the other double bond in the ring intact as shownbelow. Accordingly, all such combinations are part of this invention.

The term “low K” refers in general to a dielectric constant less thanthat of thermally formed silicon dioxide (3.9) and when used inreference to a “low-K material” it will be understood to mean a materialhaving a dielectric constant of less than 3.9.

The term “photodefinable” refers to the characteristic of a material orcomposition of materials, such as a polymer composition in accordancewith embodiments of the present invention, to be formed into, in and ofitself, a patterned layer or a structure. In alternate language, a“photodefinable layer” does not require the use of another materiallayer formed thereover, for example a photoresist layer, to form theaforementioned patterned layer or structure. It will be furtherunderstood that a polymer composition having such a characteristic beemployed in a pattern forming scheme to form a patterned film/layer orstructure. It will be noted that such a scheme incorporates an“imagewise exposure” of the photodefinable material or layer. Suchimagewise exposure being taken to mean an exposure to actinic radiationof selected portions of the layer, where non-selected portions areprotected from such exposure to actinic radiation.

The phrase “a material that photonically forms a catalyst” refers to amaterial that, when exposed to “actinic radiation” will break down,decompose, or in some other way alter its molecular composition to forma compound capable of initiating a crosslinking reaction in the polymer,where the term “actinic radiation” is meant to include any type ofradiation capable of causing the aforementioned change in molecularcomposition. For example, any wavelength of ultraviolet or visibleradiation regardless of the source of such radiation or radiation froman appropriate X-ray and electron beam source. Non-limiting examples ofsuitable materials that “photonically form catalyst” include photoacidgenerators and photobase generators such as are discussed in detailbelow. It should also be noted that generally “a material thatphotonically forms a catalyst” will also form a catalyst if heated to anappropriate temperature. Such exposures are sometimes desirable afterdeveloping a positive tone image and to fix the images post developingby blanket exposure to a suitable radiation.

The term “cure” (or “curing”) as used in connection with a composition,e.g., “a cured composition,” shall mean that at least a portion of thecrosslinkable components which are encompassed by the composition are atleast partially crosslinked. In some embodiments of the presentinvention, the crosslinking is sufficient to render the polymer filminsoluble in the developer and in some other embodiments the polymerfilm is insoluble in commonly used solvents. One skilled in the art willunderstand that the presence and degree of crosslinking (crosslinkdensity) can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA). This method determines the glasstransition temperature and crosslink density of free films of coatingsor polymers. These physical properties of a cured material are relatedto the structure of the crosslinked network. Higher crosslink densityvalues indicate a higher degree of crosslinking in the coating or film.

Monomers

Various first type of monomers as described herein which are part ofpolymer embodiments in accordance with the present invention aregenerally known in the art. In general, the polymers of this inventionencompass a wide range of first type of monomers of formula (I) asdescribed herein which contain a norbornadiene unit. Various other“polycyclic” repeating units encompassing the norbornadiene unit canalso be used which are structurally similar to the “norbornene” typemonomers of formula (IV) as further described herein as the fourth typeof monomers encompassed by the polymer embodiments of this invention. Asdefined herein, the terms “polycyclic olefin” or “polycycloolefin” meanthe same and are used interchangeably to represent several of the firstor the fourth type of monomeric compounds used to prepare the polymersof this invention. As a representative example of such a compound or amonomer is norbornadiene and is generally referred to herein as additionpolymerizable monomer (or the resulting repeating unit), that encompassat least one nortricyclene moiety such as shown herein.

Various norbornadienes of formula (I) employed in this invention can besynthesized by any of the procedures known to one skilled in the art orare themselves commercially available. The first type of monomersemployed herein as well as several of the precursor compounds may alsobe prepared by methods used to prepare similar compounds as reported inthe literature and as further described herein. See for instance, J. M.J. Frechet et al., Angew. Chem Int. Ed., 1998, 37, No. 5, 667-670 aswell as U.S. Pat. No. 5,212,043, pertinent portions of which areincorporated herein by reference.

Similarly, various other monomers of formulae (II) or (III) as describedherein are also known in the art or are themselves commerciallyavailable. Also, monomers of formulae (II) can be synthesized by any ofthe procedures known to one skilled in the art.

Finally, various fourth type of monomers as described herein which arepart of some of the polymer embodiments in accordance with the presentinvention are generally known in the art. In some embodiments, thepolymers of this invention encompass a wide range of fourth type of“polycycloolefin” repeating units. As a representative example of such acompound or a monomer is “norbornene-type” monomer and is generallyreferred to herein as addition polymerizable monomer (or the resultingrepeating unit), that encompass at least one norbornene moiety such asshown below:

The simplest norbornene-type or polycyclic olefin monomer encompassed bysome of the embodiments in accordance with the present invention isnorbornene itself, also known as bicyclo[2.2.1]hept-2-ene. However, theterm norbornene-type monomer or repeating unit is used herein to meannorbornene itself as well as any substituted norbornene(s), orsubstituted and unsubstituted higher cyclic derivatives thereof.Representative examples of such monomers include but not limited tobicyclo[2.2.2]oct-2-ene,1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene,1,4,4a,5,6,7,8,8a-octahydro-1,4-epoxy-5,8-methanonaphthalene, and thelike.

In general, the “norbornene-type” monomeric compounds employed in thisinvention are known in the literature or can be synthesized by any ofthe procedures known to one skilled in the art. Specifically, several ofthe starting materials used in the preparation of the fourth type ofmonomers used herein are known or are themselves commercially available.See for instance, U.S. Pat. Nos. 7,799,883; 8,541,523; and 8,715,900,pertinent portions of which are incorporated herein by reference.

Polymers

Embodiments in accordance with the present invention encompass polymershaving at least one repeating unit derived from a norbornadiene-typemonomer of formula (I) as defined herein, at least one repeating unitderived from a maleic anhydride-type monomer of formula (II) as definedherein and at least one repeating unit derived from a maleimide-typemonomer of formula (III) as defined herein. It should be understood thatvarious other types of monomers can also be used in addition to monomersof formulae (I), (II) and (III) to form the polymers employed in thisinvention especially the “norbornene-type” monomers of formula (IV) asfurther described herein. Such polymers can be prepared by any of themethods known in the art. Generally, such polymers are prepared by freeradical polymerization methods. See for example, U.S. Pat. No.8,715,900, which discloses ring-opened maleic anhydride polymers withalcohols (ROMA) and copolymerized with a variety of norbornene monomers.

Accordingly, in one aspect of this invention there is provided a polymercomprising one or more distinct first repeating unit represented byformula (IA), each of said first repeating unit is derived from amonomer of formula (I):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit;

each of R₁, R₂, R₃ and R₄ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,halogen —CO₂R and a group of the formula (A):

Where R is hydrogen, (C₁-C₆)alkyl or tri((C₁-C₆)alkyl)silyl; and

R_(a) is selected from the group consisting of —(CH₂)_(p)—,—(CH₂)_(q)—OCH₂— and —(CH₂)_(q)—(OCH₂CH₂)_(r)—OCH₂—, where p is aninteger from 0 to 6, q is an integer from 0 to 4 and r is an integerfrom 0 to 3;

one or more distinct second repeating unit represented by formula (IIA),said second repeating unit is derived from a monomer of formula (II):

wherein:

each of R₅ and R₆ is independently selected from the group consisting ofhydrogen, linear or branched (C₁-C₉)alkyl and fluorinated orperfluorinated(C₁-C₉)alkyl;

R₇ is selected from the group consisting of hydrogen, linear or branched(C₁-C₉)alkyl, fluorinated or perfluorinated(C₁-C₉)alkyl, and—(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4; and

one or more distinct third repeating unit represented by formula (IIIA),said third repeating unit is derived from a monomer of formula (III):

wherein:

each of R₅ and R₉ is independently selected from the group consisting ofhydrogen, linear or branched (C₁-C₉)alkyl and fluorinated orperfluorinated(C₁-C₉)alkyl;

R₁₀ is selected from the group consisting of hydrogen, linear orbranched (C₁-C₁₆)alkyl, (C₃-C₉)cycloalkyl,(C₃-C₉)cycloalkyl(C₁-C₁₀)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₄)alkyl,(C₁-C₁₆)alkylCO₂R, (C₁-C₁₆)alkylCH₂OR, (C₆-C₁₀)arylCO₂R and(C₆-C₁₀)arylCH₂OR; where R is hydrogen, (C₁-C₆)alkyl ortri((C₁-C₆)alkyl)silyl.

Advantageously, the polymers of this invention encompasses variousmonomeric repeat units wherein molar ratio of repeating unit of formula(IA) is substantially same as the combined molar ratios of repeatingunits of formulae (IIA) and (IIIA). That is, as noted earlier, the molarratios of combined monomeric units of formula (IA) are generally same asthe combined molar ratios of monomeric repeat units of formulae (IIA)and (IIIA). In other words, the monomeric repeat units of formula (IA)and monomeric units of formulae (IIA) and (IIIA) generally alternate asalready mentioned above. See for example, W. D. Beck, et al., J.Macromol. Sci. Chem., A5(3) 491-506 (1971).

It should further be noted that the polymer of this invention furthercomprises a repeat unit of formula (IB) derived from the monomer offormula (I):

wherein R₁, R₂, R₃ and R₄ are each as defined herein.

As noted, the polymers of this invention generally encompasses at leastone monomer each of formulae (I), (II) and (III). However, the polymerof this invention can encompass one or more distinct monomer of formulae(I). Similarly, more than one distinct monomer of formula (II) can alsobe used as well as more than one distinct monomer of formula (III) canbe employed. Thus, the polymers used to form the photosensitive orphotoimagable compositions of this invention can be a terpolymercontaining at least one monomer of each of formulae (I) to (III); atetrapolymer containing at least one monomer each of formulae (I) to(IV); a tetrapolymer containing at least one monomer each of formulae(I) to (III) and an additional distinct monomer selected either fromformulae (I), (II) or (III); and so on. All such various combinationsare part of this invention. Accordingly, in one of the embodiments ofthis invention, the polymer of this invention is a terpolymer havingrepeat units derived from one monomer each of formulae (I), (II) and(III). In another embodiment of this invention, the polymer of thisinvention is a tetrapolymer having repeat units derived from one monomereach of formulae (I), (II), (III) and (IV).

In a further embodiment of this invention the polymer of this inventionis a tetrapolymer having two distinct repeat units derived from twodifferent monomers of formula (I) and one of each repeat units derivedfrom respective monomers of formulae (II) and (III). In yet anotherembodiment of this invention the polymer of this invention is atetrapolymer having one each of repeat units derived from respectivemonomers of formulae (I) and (II) and two distinct repeat units derivedfrom two distinct monomers of formula (III). In another embodiment ofthis invention the polymer of this invention is a tetrapolymer havingone each of repeat units derived from respective monomers of formulae(I) and (III) and two distinct repeat units derived from two distinctmonomers of formula (II).

In another embodiment, the polymer of this invention comprises a seconddistinct repeat unit of formula (IIB) derived from a monomer of formula(II):

wherein R₅ and R₆ are as defined hereinabove.

In another embodiment of this invention, the polymer of this inventionfurther comprises one or more distinct fourth repeat unit of formula(IVA) derived from a monomer of formula (IV):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit;

m is an integer 0, 1 or 2;

each of R₁₁, R₁₂, R₁₃ and R₁₄ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₅-C₁₀)heteroaryl,(C₅-C₁₀)heteroaryl(C₁-C₃)alkyl, hydroxy, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,—(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl, (C₆-C₁₀)aryloxy,(C₅-C₁₀)heteroaryloxy, halogen, —(CH₂)_(a)—CO₂R, where R is hydrogen,linear or branched (C₁-C₆)alkyl, (C₅-C₈)cycloalkyl, (C₆-C₁₀)aryl or(C₇-C₁₂)aralkyl (C₁-C₆)acyloxy, and a group of the formula (A):

Where R_(d) is selected from the group consisting of —(CH₂)_(p)—,—(CH₂)_(q)—OCH₂— or —(CH₂)_(q)—(OCH₂CH₂)_(r)—OCH₂—, where p is aninteger from 0 to 6, q is an integer from 0 to 4 and r is an integerfrom 0 to 3.

In a further embodiment of this invention the polymer of this inventioncomprises one or more distinct repeating units of formula (IA) wherein,each of R₁, R₂, R₃ and R₄ is independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₁-C₁₂)alkyland phenyl(C₁-C₃)alkyl.

In yet another embodiment of this invention the polymer of thisinvention comprises one or more distinct repeating units of formula(IIA) wherein, R₅ and R₆ independently of each other selected fromhydrogen and methyl; and R₇ is selected from hydrogen, methyl, ethyl,n-propyl, iso-propyl and n-butyl.

In yet another embodiment of this invention the polymer of thisinvention comprises one or more distinct repeating units of formula(IIIA) wherein, R₈ and R₉ independently of each other selected fromhydrogen and methyl; and R₁₀ is selected from hydrogen, methyl, ethyl,n-propyl, iso-propyl, n-butyl, cyclopentyl, cyclohexyl, cycloheptyl,phenyl, benzyl and phenethyl.

In yet another embodiment of this invention the polymer of thisinvention comprises one or more distinct repeating units of formula(IVA) wherein:

m is 0;

each of R₁₁, R₁₂, R₁₃ and R₁₄ is independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₁-C₁₂)alkyl,phenyl(C₁-C₃)alkyl, —(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₄)alkyl, where ais 1 or 2, b is 2 to 4 and cis 2 or 3.

As noted above, various monomers within the scope of formula (I) can beemployed to form the polymers of this invention. Accordingly, one ormore such exemplary monomers that can be employed to make the polymeraccording to this invention can be selected from the group consistingof:

Turning now to second repeating unit to form the polymer of thisinvention it is contemplated that any maleic anhydride derivative offormula (II) can be used as a monomer, including maleic anhydrideitself. Exemplary monomers of such type include but not limited to thoseselected from the group consisting of:

Turning now to third repeating unit to form the polymer of thisinvention it is contemplated that any maleimide derivative of formula(III) can be used as a monomer, including maleimide itself. Exemplarymonomers of such type include but not limited to those selected from thegroup consisting of:

In the above, 1-(4-hydroxyphenyl)-1H-pyrrole-2,5-dione, thecorresponding ortho- and meta-substituted isomers can also be used,i.e., 1-(2-hydroxyphenyl)-1H-pyrrole-2,5-dione and1-(3-hydroxyphenyl)-1H-pyrrole-2,5-dione. The same applies to otherphenyl substituted maleimides shown below.

Finally, any of the known “norbornene-type” monomers of formula (IV) canbe used to make the polymers of this invention encompassing the repeatunits of formula (IVA). Exemplary monomers which form such fourthrepeating unit include but not limited to those monomers selected fromthe group consisting of:

In yet another embodiment of this invention the polymer according tothis invention contain various combinations of monomer repeat units offormulae (IA), (IB), (IIA), (IIB), (IIIA) and (IVA). Non-limitingexamples of such specific polymers within the scope of this invention isselected from the group consisting of:

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol andN-phenylmaleimide (42:28:30 molar ratio);

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol and maleimide(38:49:13 molar ratio);

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol andN-cyclohexyl-maleimide (50:27:23 molar ratio);

a tetrapolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON),maleic anhydride in which maleic anhydride repeating unit is ring openedwith methanol and N-phenylmaleimide (33:10:24:33 molar ratio);

a tetrapolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol,N-cyclohexylmaleimide (N-CyHexMI) and maleimide (53 mole percent of NBDand combined 47 mole percent of MA/N-CyHexMI and MI); and

a tetrapolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol, N-phenylmaleimideand maleimide.

Useful monomers for embodiments in accordance with the present inventionare described generally hereinabove. As also noted above the polymer ofthis invention generally encompasses equal molar amounts of repeat unitsderived from one or more monomers of formulae (I) and (IV), if present,and repeat units derived from one or more monomers of formulae (II) and(III). That is to say that the total molar amounts of one or moredistinct types of monomers of formula (I) and (IV) and the total molaramounts of one or more distinct types of monomers of formula (II) and(III) are generally the same. However, in some embodiments the totalmole ratios of repeat units of formulae (IA) and (IB), if present, and(IVA) can be higher or lower than 50 mole percent, and thus the totalmole ratios of repeat units of formulae (IIA) and (IIB), if present, and(IIIA) can be different than 50 mole percent. Accordingly, in someembodiments the total mole ratios of repeat units of formulae (IA) and(IB), if present, and (IVA), if present, is in the range of from 30 to60 mole percent, in other embodiments the combined mole percent ofrepeat units of formulae (IA) and (IB), if present, and (IVA), ifpresent, is in the range of from 40 to 60 mole percent and in otherembodiments it can be from 45 to 55 mole percent. Accordingly, in someembodiments the total mole ratios of repeat units of formulae (IIA) and(IIB), if present, and (IIIA) is in the range of from 40 to 70 molepercent, in other embodiments the combined mole percent of repeat unitsof formulae (IIA) and (IIB), if present, and (IIIA) is in the range offrom 40 to 60 mole percent and in other embodiments it can be from 45 to55 mole percent.

Advantageously, it has now been found that the polymers of thisinvention contain at least three mole percent of repeat units of formula(IIIA). In some other embodiments the mole percent of repeat units offormula (IIIA) is in the range of from 4 mole percent to 30 molepercent, in some other embodiments it is in the range of from 5 to 20mole percent and in other embodiments it is in the range of from 8 to 15mole percent. Similarly, the total mole percent of repeat units offormula (IIA) and (IIB), if present, is in the range of from 20 molepercent to 60 mole percent, in some other embodiments it is in the rangeof from 25 to 50 mole percent and in other embodiments it is in therange of from 30 to 40 mole percent. The total mole percent of repeatunits of formula (IA) and (IB), if present, is in the range of from 30mole percent to 60 mole percent, in some other embodiments it is in therange of from 35 to 55 mole percent and in other embodiments it is inthe range of from 40 to 50 mole percent. Finally, the mole percent ofrepeat units of formula (IVA), if present, is in the range of from 0mole percent to 20 mole percent, in some other embodiments it is in therange of from 5 to 15 mole percent and in other embodiments it is in therange of from 10 to 12 mole percent.

Generally speaking, as to various possible substituents defined for R₁,R₂, R₃, R₄, it should be noted that such substituents can broadly bedefined as “hydrocarbyl” group. As defined hereinabove, such definitionof “hydrocarbyl” group includes any C₁ to C₃₀ alkyl, aryl, aralkyl,alkaryl, cycloalkyl, or heteroalkyl group. Representative alkyl groupsinclude, but are not limited to, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl,heptyl, octyl, nonyl, and decyl. Representative cycloalkyl groupsinclude, but are not limited to, adamantyl, cyclopentyl, cyclohexyl, andcyclooctyl. Representative aryl groups include, but are not limited to,phenyl, naphthyl, and anthracenyl. Representative aralkyl groupsinclude, but are not limited to, benzyl and phenethyl. In addition, itshould be noted that the hydrocarbyl groups mentioned above can besubstituted, that is to say at least one of the hydrogen atoms can bereplaced with, for example, (C₁-C₁₀)alkyl, haloalkyl, perhaloalkyl,aryl, and/or cycloalkyl group(s). Representative substituted cycloalkylgroups include, among others, 4-t-butylcyclohexyl and2-methyl-2-adamantyl. A non-limiting representative substituted arylgroup is 4-t-butylphenyl.

Polymer Preparation

In general, the polymers of this invention can be prepared by any one ofthe known procedures in the art. For instance, one or more monomers offormula (I) as described herein can be polymerized along with one ormore monomers of formulae (II) and (III) to form the polymers of thisinvention containing the respective monomeric repeat units asrepresented by formulae (IA), (IB), (IIB) and (IIIA) which are calledhereinafter as “COMA-MI” polymers. The maleic anhydride repeat units offormula (IIB) can also be ring opened either partially or completely bysubjecting to suitable reaction conditions to form repeat units offormula (IIA) as described herein, which are called hereinafter as“ROMA-MI” polymers. Further, one or more monomers of formula (IV) can befurther included in these polymerization reactions to form polymercompositions which would additionally include repeat units of formula(IVA). Again, any of the polymerization methods can be employed to formthe polymer compositions of this invention. In general, thepolymerization can be carried out either in solution using a desirablesolvent or in mass, and in both instances, suitably in the presence of acatalyst or an initiator. Any of the known catalyst system which bringsabout the polymerization of the monomers of formula (I) with monomers offormula (II) can be used along with monomers of formula (III), furtherin combination with monomers of formula (IV).

Advantageously, it has now been found that polymers of this inventioncan be prepared by any of the known free radical polymerizationprocedures. Typically in a free radical polymerization process, themonomers are polymerized in a solvent at an elevated temperature (about50° C. to about 150° C.) in the presence of a free radical initiator.Suitable initiators include but are not limited to azo compounds andperoxides. Non-limiting examples of azo compounds includeazobisisobutyronitrile (AIBN), (E)-dimethyl2,2′-(diazene-1,2-diyl)bis(2-methylpropanoate) (AMMP),(E)-2,2′-(diazene-1,2-diyl)bis(2,4-dimethylpentanenitrile (ADMPN),1,1′-azobis(cyclohexanecarbonitrile) (ABCN), azobisisocapronitrile andazobisisovaleronitrile. Non-limiting examples of peroxides includehydrogen peroxide, tert-butylhydroperoxide, di-(tertiary)-butylperoxide, benzoyl peroxide, lauryl peroxide, and methyl ethyl ketoneperoxide. As noted, any of the other known initiators, including otherazo compounds and peroxides can also be used in this polymerizationprocess.

Suitable polymerization solvents for the aforementioned free radicalpolymerization reactions include hydrocarbon, haloalkane, ketone andaromatic solvents, among other suitable solvents. Exemplary hydrocarbonsolvents include but are not limited to alkanes and cycloalkanes such aspentane, hexane, heptane and cyclohexane. Exemplary haloalkane solventsinclude but or not limited to dichloromethane, chloroform, carbontetrachloride, ethylchloride, 1,1-dichloroethane, 1,2-dichloroethane,1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, 1-chloropentane, Freon™ 112 halocarbonsolvent. Exemplary ketone solvents include cyclopentanone andcyclohexanone. Exemplary aromatic solvents include but are not limitedto benzene, toluene, xylene, mesitylene, chlorobenzene, ando-dichlorobenzene. Other organic solvents such as diethyl ether,tetrahydrofuran, acetates (e.g., ethyl acetate) and other esters,lactones, ketones and amides, including N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), propyleneglycolmonomethylether acetate (PGMEA), are also useful. Mixtures of one ormore of the foregoing solvents can be utilized as a polymerizationsolvent. In some embodiments the solvents employed include cyclohexane,toluene, mesitylene, dichloromethane and 1,2-dichloroethane.

As noted, the polymer as obtained above is then subjected to suitablereaction conditions to ring open the maleic anhydride repeat units offormula (IIB) to form the repeat units of formula (IIA), the ROMApolymers employed in the compositions of this invention. Any of theknown methods which would bring about such a ring opening can beemployed in this method of the invention. Non-limiting examples of suchring opening reactions include reacting the polymer with a suitablealcohol optionally in the presence of a suitable base or an acid.Non-limiting examples of alcohols include methanol, ethanol, n-propanol,iso-propanol, n-butanol, iso-butanol, tert-butanol, pentanol, hexanol,octanol, fluoroalkanol, methoxyethanol, methoxyethoxymethanol,methoxyethoxyethanol, butoxyethoxyethanol, and the like. Non-limitingexamples of base include sodium hydroxide, lithium hydroxide, potassiumhydroxide, cesium hydroxide, ammonia, ammonium hydroxide, magnesiumhydroxide, calcium hydroxide, barium hydroxide, and the like. Variousother known organic bases can also be employed. Representative examplesof which include, tetramethylammonium hydroxide (TMAH),tetraethylammonium hydroxide (TEAH), pyridine, imidazole, and the like.Non-limiting examples of acids include acetic acid, trifluoroaceticacid, sulfuric acid, hydrochloric acid, methanesulfonic acid,trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonicacid, and mixtures thereof. As noted, in some embodiments the ringopening can also be carried without any acid or base.

The aforementioned ring opening reactions can be carried out using anyof the known methods in the art. Typically, such reactions are carriedout in a suitable solvent or a mixture of solvents in the presence of abase and an alcohol. Examples of base and alcohol are already describedabove. Non-limiting examples of solvents include tetrahydrofuran (THF),acetonitrile, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO),N-methylpyrrolidone (NMP), propyleneglycol monomethylether acetate(PGMEA), ethyl acetate, methyl ethyl ketone (MEK), toluene, hexane,water, and mixtures thereof. The reaction can also be carried out in thepresence of reacting alcohol alone, such as for example, methanol,ethanol, isopropanol, and the like. Mixtures of any of the foregoingsolvents can also be used. The reaction can be carried out at suitabletemperature including ambient, sub-ambient and super-ambient conditions.Typically, the reaction temperature employed is in the range of fromabout 40 to 120° C. and in certain embodiments the temperature can be inthe range of 50 to 90° C. or from about 55 to 80° C. and in some otherembodiments it can be in the range of 60 to 70° C.

The ROMA polymers so formed in accordance with this invention, dependingupon contacting with such aforementioned reagents will cause eithercomplete or partial ring open of the maleic anhydride repeating units toform a repeat unit of formula (IIA). Thus, such ROMA polymers may have arandomly ordered repeat units of formula (IA), (IB), (IIA), (IIB) and(IIIA), wherein the repeat units of formula (IIA) may include acombination of diacid (i.e., R₇ is hydrogen) or a monoester (i.e., R₇ isother than hydrogen) depending upon the degree of esterification withthe alcohol. Thus in accordance with this aspect of the embodiment ofthis invention, the ring opened portion of the maleic anhydride repeatunit of formula (IIA) is in the order of from about 80 mole percent toabout 100 mole percent; in some other embodiments it is higher than 90mole percent; in some other embodiments it is higher than 95 molepercent; and in some other embodiments it is higher than 98 molepercent. In some other embodiments more than 99 mole percent of maleicanhydride units are ring opened. The amount of free acid present can betailored by controlling the degree of esterification with an alcohol.Thus in one of the embodiments the amount of diacid present in themaleic anhydride repeat units of formula (IIA) is from about 0 molepercent to about 100 mole percent; in some other embodiments it is fromabout 20 mole percent to about 80 mole percent; in some otherembodiments it is from about 40 mole percent to about 60 mole percent;and in some other embodiments it is from about 45 mole percent to about55 mole percent. That is to say, when 50 mole percent of the repeat unitof formula (IIA) is diacid, the remaining portions of the repeat unitsare esterified, thus portions of the repeat units is mono-esterified togive a cumulative total of 50% of the repeat units to be esterified.Accordingly, it should also be noted that it is possible that certainsegments of the polymer chain may contain diesterified fully ring openedmaleic anhydride repeat units. That is to say that in the repeat unitsof formula (IIA) the free acid is esterified and R₇ is not hydrogen.

Accordingly, the polymers employed in the compositions of this inventionare therefore generally formed from the hydrolysis of the polymerscontaining the repeat units of formula (IA) and formula (IIB) along withrepeat units of formula (IIIA) and (IVA), if present, (COMA), whichafter hydrolysis results in ring-opened polymers containing generallythe repeat units of formula (IA) and (IIA), the ROMA polymers. The ROMApolymers as employed in this invention generally exhibit a weightaverage molecular weight (M_(w)) of at least about 20,000. In anotherembodiment, the polymer of this invention has a M_(w) of at least about30,000. In yet another embodiment, the polymer of this invention has aM_(w) of at least about 40,000. In some other embodiments, the polymerof this invention has a M_(w) of at least about 50,000. In some otherembodiments, the polymer of this invention has a M_(w) higher than50,000. The weight average molecular weight (M_(w)) of the polymer canbe determined by any of the known techniques, such as for example, bygel permeation chromatography (GPC) equipped with suitable detector andcalibration standards, such as differential refractive index detectorcalibrated with narrow-distribution polystyrene standards.

Photoimagable Compositions

Thus, in accordance with the practice of this invention there is furtherprovided a composition comprising:

a polymer comprising one or more distinct first repeating unitrepresented by formula (IA), each of said first repeating unit isderived from a monomer of formula (I):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit;

each of R₁, R₂, R₃ and R₄ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,—CO₂R and halogen; where R is (C₁-C₆)alkyl or tri((C₁-C₆)alkyl)silyl;

one or more distinct second repeating unit represented by formula (IIA),said second repeating unit is derived from a monomer of formula (II):

wherein:

each of R₅ and R₆ is independently selected from the group consisting ofhydrogen, linear or branched (C₁-C₉)alkyl and fluorinated orperfluorinated(C₁-C₉)alkyl;

R₇ is selected from the group consisting of hydrogen, linear or branched(C₁-C₉)alkyl, fluorinated or perfluorinated(C₁-C₉)alkyl,

and —(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4; and

one or more distinct third repeating unit represented by formula (IIIA),said third repeating unit is derived from a monomer of formula (III):

wherein:

each of R₅ and R₉ is independently selected from the group consisting ofhydrogen, linear or branched (C₁-C₉)alkyl and fluorinated orperfluorinated(C₁-C₉)alkyl;

R₁₀ is selected from the group consisting of hydrogen, linear orbranched (C₁-C₉)alkyl, (C₃-C₅)cycloalkyl, (C₃-C₉)cycloalkyl(C₁-C₄)alkyl,(C₆-C₁₀)aryl and (C₆-C₁₀)aryl(C₁-C₄)alkyl;

and wherein molar ratio of repeating unit of formula (IA) issubstantially same as the combined molar ratios of repeating units offormulae (IIA) and (IIIA);

a photoactive compound;

a cross-linking agent; and

a carrier solvent.

Any of the polymers as described herein can be employed in thecompositions of this invention.

In a further aspect of this invention there is also provided acomposition comprising:

a polymer comprising one or more distinct first repeating unitrepresented by formula (IA), each of said first repeating unit isderived from a monomer of formula (I):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit;

each of R₁, R₂, R₃ and R₄ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,—CO₂R, halogen and a group of formula (A):

where R is (C₁-C₆)alkyl or tri((C₁-C₆)alkyl)silyl; and

R_(a) is selected from the group consisting of —(CH₂)_(p)—,—(CH₂)_(q)—OCH₂— and —(CH₂)_(q)—(OCH₂CH₂)_(r)—OCH₂—, where p is aninteger from 0 to 6, q is an integer from 0 to 4 and r is an integerfrom 0 to 3; and

one or more distinct second repeating unit represented by formula (IIA),said second repeating unit is derived from a monomer of formula (II):

wherein:

each of R₅ and R₆ is independently selected from the group consisting ofhydrogen, linear or branched (C₁-C₉)alkyl and fluorinated orperfluorinated(C₁-C₉)alkyl;

R₇ is selected from the group consisting of linear or branched(C₄-C₁₆)alkyl, fluorinated or perfluorinated(C₁-C₁₆)alkyl, and—(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4; and

a photoactive compound;

a cross-linking agent; and

a carrier solvent.

In this aspect of the invention the polymers that are employed in makingthe compositions are copolymers derived from norbornadiene monomers andmaleic anhydride which is ring opened by a variety of alcohols asdisclosed herein. Any of the copolymers as described herein which arewithin the scope of this aspect of the invention can be employed.

Exemplary copolymers which are suitable in this invention without anylimitation include the following:

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with n-decanol;

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with n-butoxyethoxyethanol;

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with n-dodecanol;

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with n-hexyloxyethoxyethanol;

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with octanol; and

a copolymer of norbornadiene (NBD) and maleic anhydride in which maleicanhydride repeating unit is ring opened with methoxyethoxyethanol.

In yet another embodiment of this aspect of the invention, various ter-and tetrapolymers derived from the above noted copolymers and any one ormore of the norbornene monomers as described herein can also beemployed.

a terpolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON)and maleic anhydride in which maleic anhydride repeating unit is ringopened with n-decanol;

a terpolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON)and maleic anhydride in which maleic anhydride repeating unit is ringopened with n-butoxyethoxyethanol;

a terpolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON)and maleic anhydride in which maleic anhydride repeating unit is ringopened with n-hexyloxyethoxyethanol;

a terpolymer of norbornadiene (NBD),norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB) andmaleic anhydride in which maleic anhydride repeating unit is ring openedwith octanol;

a terpolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON)and maleic anhydride in which maleic anhydride repeating unit is ringopened with n-undecanol; and

a tetrapolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON),5-phenethylbicyclo[2.2.1]hept-2-ene (PENB) and maleic anhydride in whichmaleic anhydride repeating unit is ring opened withmethoxyethoxyethanol.

As mentioned above, the polymer compositions of this invention furthercontains a photoactive compound (PAC). Any of the PACs known to oneskilled in the art which would bring about the desired results asfurther discussed herein can be employed in the composition of thisinvention. Broadly speaking, the PAC that can be employed in thisinvention is a photosensitive compound which when exposed to suitableradiation undergoes a chemical transformation such that the resultingproduct is generally more soluble in a developing solvent, such as forexample, alkali solution thus facilitating the exposed regions todissolve more readily than the unexposed regions. As noted, thecomposition of this invention further encompass an epoxy resin and asolvent. Further, such compositions are capable of forming films usefulas self-imagable layers in the manufacture of microelectronic andoptoelectronic devices. That is to say that when image-wise exposed toactinic radiation, such layers (or films) can be developed to form apatterned film, where such pattern is reflective of the image throughwhich the film was exposed.

In this manner, structures can be provided that are, or are to become, apart of such microelectronic and/or optoelectronic devices. For example,such films may be useful as low-K dielectric layers in liquid crystaldisplays or in microelectronic devices. It will be noted that suchexamples are only a few of the many uses for such a self-imagable film,and such examples do not serve to limit the scope of such films or thepolymers and polymer compositions that are used to form them.

Generally, the PACs that are suitable in this invention contain adiazo-quinone group of formula (B):

Non-limiting examples of such a photoactive compound (PAC) can include agroup, such as, 1,2-naphthoquinonediazide-5-sulfonyl moiety and/or a1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structuralformulae (Va) and (Vb), respectively:

Other such photoactive moieties, among others, include sulfonylbenzoquinone diazide group represented by structural formula (Vc):

Generally, the functional groups of formulae (Va), (Vb) and/or (Vc) areincorporated into the photosensitive composition as an esterificationproduct of the respective sulfonyl chloride (or other reactive moiety)and a phenolic compound, such as one or more of the exemplary compoundsrepresented below collectively as structural formulae (VIa) to (VIag).Thus, any one, or any mixture of two or more of such esterificationproducts are combined with the resin in forming the photosensitive resincompositions of the present invention. In the formulae (VIa) to (VIag)below, Q may represent any of the structures (Va), (Vb) or (Vc).Advantageously, when a portion of a film or a layer of thephotosensitive composition is exposed to appropriate electromagneticradiation, these esterification products generate a carboxylic acidwhich enhances the solubility of such exposed portion in an aqueousalkali solution as compared to any unexposed portions of such film.Generally, such photosensitive materials are incorporated into thecomposition in an amount from 1 to 50 parts by weight material to 100parts by weight resin. Where the specific ratio of the photosensitivematerial to resin is a function of the dissolution rate of exposedportions as compared to unexposed portions and the amount of radiationrequired to achieve a desired dissolution rate differential.

In the above listed PACs of formulae (VIa) to (VIag), Q refers to anyone of photoactive moieties of formulae (Va), (Vb) or (Vc) or hydrogen,but at least one of these Q in each of these structures is (Va), (Vb) or(Vc). Several of the PACs listed above are commercially available. Forexample, PAC-5570 of formula (VIc) (St. Jean Photochemicals Inc.,Quebec, Canada), SCL6 of formula (VId) (Secant Chemicals Inc.,Winchendon, Mass., USA), Tris-P 3M6C-2-201 of formula (VIo) (alsoreferred to herein as TrisP), collectively TS-200, TS-250 and TS-300 offormula (VIa), and 4NT-300 of formula (VIe) (all from Toyo Gosei Co.Ltd., Chiba, Japan). It should be noted that for PACs of the typesTS-200, TS-250 and TS-300, the degree of substitution of Qs also variesbased on the product used. For instance, TS-200 is substituted with 67%of Q, TS-250 is substituted with 83% of Q, and TS-300 with 100% of Q,the unsubstituted portion being hydrogen. Again, Q in each of theseinstances refers to one of group (Va), (Vb) or (Vc).

The amount of PACs incorporated into the polymer compositions dependsupon the type of polymer used and to the dosage level of the exposurecontemplated. The amount can vary generally from about 5 to 50 parts per100 parts by weight of the polymer and typically from about 10 to about30 parts by weight, although other advantageous amounts of suchmaterials are also appropriate and within the scope of the presentinvention.

Exemplary epoxies and other cross-linking additives, as mentioned above,include, but are not limited to, bisphenol A epoxy resin (LX-1—DaisoChemical Co., Osaka, Japan),2,2′-((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)(Techmore VG3101L—Mitsui Chemical Inc.), trimethylolpropanetriglycidylether (TMPTGE-CVC Specialty Chemicals, Inc.), and1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane(DMS-E09—Gelest, Inc.), liquid epoxy resins (D.E.R.™ 732, where n=8 to10, and D.E.R.™ 736, where n=4 to 6—both from Dow Chemical Company),bis(4-(oxiran-2-ylmethoxy)phenyl)methane (EPON™ 862, Hexion SpecialtyChemicals, Inc.), triglycidyl ether of poly(oxypropylene)epoxide etherof glycerol (commercially available as Heloxy 84 or GE-36 from MomentiveSpecialty Chemicals Inc.), 2-((4-(tert-butyl)phenoxy)methyl)oxirane(commercially available as Heloxy 65 from Momentive Specialty ChemicalsInc.) and silicone modified epoxy compound (commercially available asBY16-115 from Toray-Dow Corning Silicone Co., Ltd.) as shown below:

-   triglycidyl ether of poly(oxypropylene)epoxide ether of glycerol,    where n is from 6 to 10, commercially available as Heloxy 84 or    GE-36 from Momentive Specialty Chemicals Inc.;

-   2-((4-(tert-butyl)phenoxy)methyl)oxirane, commercially available as    Heloxy 65 from Momentive Specialty Chemicals Inc.; and

-   Silicone modified epoxy compound commercially available as BY16-115    from Toray-Dow Corning Silicone Co., Ltd.

-   available from Nippon Kayaku Co., Ltd.

-   available from Daicel Corp.

Other cross-linking agents that can be used in the compositions of thisinvention include the following:

Still other exemplary epoxy resins or cross-linking additives include,among others Araldite MTO163 and Araldite CY179 (manufactured by CibaGeigy); and EHPE-3150, Epolite GT300 and (manufactured by DaicelChemical).

The amount of epoxy compound may also vary as noted for PACs dependingupon the base polymer employed in the composition and the amount canalso vary depending upon the intended result. The amount can varygenerally from about 1 to 50 parts by weight per 100 parts of thepolymer and typically from about 2 to about 30 parts by weight, althoughother advantageous amounts of such materials are also appropriate andwithin the scope of the present invention. In addition, one or moredifferent types of epoxy compounds as enumerated herein can be used inthe composition of this invention and the amounts of each can thus bevaried as needed.

Advantageously, it has now been found that polymer compositions of thisinvention provide several desirable properties especially when comparedto several of the polymers reported in the literature for similarapplications. For instance, it has been observed that several of thepolymers as described herein exhibit very low dark field loss (DFL)making them more desirable for positive tone (PT) applications. As usedherein, the term DFL or the unexposed area film thickness loss is ameasure of the film thickness loss after image-wise exposure to suitableactinic radiation and developing in a suitable developer. That is, thepolymer compositions of this invention are cast into films, the filmthicknesses before and after development in an unexposed region of thefilm are measured and reported as percent loss of the film thickness inareas of the film that was not exposed to the radiation. Generally,higher the percent of DFL, poorer the performance of the polymercomposition, which means that the unexposed areas of the film are moresusceptible to the developed and thus dissolves in the developer. Inaddition, the measured DFL also depends on the developed time employed.Generally, longer the develop time higher the DFL.

Surprisingly, the compositions of this invention exhibit very low DFL inthat the unexposed area of the film is not lost even at higher developtime. Accordingly, in some embodiments of this invention the DFL of thecompositions may be less than about 20 percent; in some otherembodiments DFL can be less than 25 percent; and in some otherembodiments the DFL may be in the range of from about 0 percent to 30percent. At the same time the develop time for the compositions of thisinvention can generally range from about 10 seconds to about 80 seconds;in some other embodiments the develop time can range from about 20seconds to about 60 seconds; and in some other embodiments the developtime can range from about 30 seconds to about 40 seconds.

In addition, advantageously it has also been found that the compositionsof this invention exhibit excellent dissolution rate in the developingsolvent, such as for example, aqueous based alkali developer, includingtetramethylammonium hydroxide (TMAH), among other known aqueousdevelopers. This can further be tailored based on the molar content ofthe free carboxylic acid group present in the maleic repeat units offormula (IIA) in the polymer. Generally, it has now been found that byjudicious selection of the molar ratio of ring opened maleic anhydriderepeat units it is now possible to control the dissolution rate of thecomposition of this invention to the desirable range. Furthermore, thecompositions of this invention retain much needed lithographicresolution, photospeed and high degree of chemical resistance, amongvarious other desirable properties.

More advantageously and surprisingly, it has also been found that thecompositions of this invention exhibit improved thermomechanicalproperties. For instance, the compositions of this invention exhibitvery high thermal stability, i.e., higher than 300° C. Therefore, thecompositions of this invention can be employed in applications wheresuch high temperature stabilities are required as further demonstratedby specific examples that follow. In addition, the compositions of thisinvention also exhibit excellent mechanical properties and form highresolution images after “image-wise” exposed to suitable actinicradiation.

In addition, various other additives/components can be added to thecomposition of this invention, which is used for the formation of thephotoimagable layer such that its mechanical and other properties can betailored as desired. Also, other additives can be used to alter theprocessability, which include increase the stability of the polymer tothermal and/or light radiation. In this regard, the additives caninclude, but are not limited to, crosslinkers, photosensitizers,antioxidants, adhesion promoters, surfactants, thermal acid and/orthermal base generator, such as CXC 1761 from King Industries, Inc.,photo acid and/or photo base generator, catalyst scavengers,stabilizers, reactive diluents, and the like. Any of these additives canbe used as a mixture in any combination thereof.

Advantageously, it has now been found that use of a base generator, suchas a thermal base generator (TBG) or a photo base generator (PBG)improves generally overall performance of the composition of thisinvention, such as for example, shelf-life and thermomechanicalproperties of the cured films obtained therefrom as evidenced from thespecific examples described hereinbelow. Accordingly, in someembodiments of this invention the compositions of this inventionencompasses one or more PBG. In some other embodiments of this inventionthe composition of this invention encompasses one or more thermal basegenerators. Any of the known TBG or PBG in an appropriate amount can beemployed in the composition of this invention which will bring about theintended change. The amount of TBG and/or PBG employed can varygenerally from about 1 to 20 parts by weight per 100 parts of thepolymer and typically from about 2 to about 10 parts by weight, althoughother advantageous amounts of such materials are also appropriate andwithin the scope of the present invention. In addition, as noted, one ormore different types of PBG and/or TBG can be used in the composition ofthis invention and the amounts of each can thus be varied as needed.

Representative examples of TBGs and/or PBGs that can be used in thecompositions of this invention without any limitation are enumeratedbelow:

-   1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl    1H-imidazole-1-carboxylate, commercially available as WPBG-140 from    Wako Specialty Chemicals;

-   1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl cyclohexylcarbamate,    commercially available as WPBG-174 from Wako Specialty Chemicals;

-   2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one,    commercially available as Irgacure-369 from BASF; and

-   2-(1H-imidazol-1-yl)-1-phenylethan-1-one.

In some embodiments of the composition of this invention the epoxiesthat can be used in the composition of this invention without anylimitation is selected from the group consisting of:

-   -   triglycidyl ether of poly(oxypropylene)epoxide ether of glycerol        (GE-36);    -   trimethylolpropane triglycidylether;    -   bisphenol A epichlorohydrin based epoxy resin;    -   polypropylene glycol epichlorohydrin based epoxy resin (D.E.R.™        732);    -   bis(4-(oxiran-2-ylmethoxy)phenyl)methane (EPON 862);    -   glycidyl ether of para-tertiary butyl phenol (Heloxy 65);    -   polyethylene glycol diglycidyl ether (PEGDGE);    -   2,2′-((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)        (VG3101L); and    -   polypropylene glycol diglycidyl ether (PPGDGE);    -   and a mixture in any combination thereof.

The polymer compositions in accordance with the present invention mayfurther contain optional components as may be useful for the purpose ofimproving properties of both the composition and the resulting layer,for example the sensitivity of the composition to a desired wavelengthof exposure radiation. Examples of such optional components includevarious additives such as a dissolution promoter, a surfactant, a silanecoupling agent, a leveling agent, an antioxidant, a fire retardant, aplasticizer, a crosslinking agent or the like. Such additives include,but are not limited to, bisphenol A and 5-norbornene-2,3-dicarboxylicacid as a dissolution promoter, a silicone surfactant such as TSF4452(Toshiba Silicone Co., Ltd) or any other suitable surfactant such asMegaface F-556, a nonionic or anionic fluorinated oligomer withhydrophilic and lipophilic group from DIC Corp. a silane coupling agentsuch as γ-aminopropyl triethoxysilane, a leveling agent, such asγ-(methacryloyloxy propyl) trimethoxysilane or FC-4432, 2-propenoicacid, 2-[methyl[(nonafluorobutyl)sulfonyl]amino]ethyl ester, telomerwith methyloxirane polymer with oxirane di-2-propenoate andmethyloxirane polymer with oxirane mono-propenoate from DIC,antioxidants such as pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGANOX™ 1010from BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl esterbenzenepropanoic acid (IRGANOX™ 1076 from BASF) and thiodiethylenebis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (IRGANOX™ 1035from BASF), a fire retardant such as a trialkyl phosphate or otherorganic phosphoric compound and a plasticizer such as, poly(propyleneglycol).

Non-limiting examples of aforementioned various otheradditives/components are selected from the group consisting of thefollowing, commercially available materials are indicated by suchcommercial names.

-   trimethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonly known    as 3-glycidoxypropyl trimethoxysilane (KBM-403E from Shin-Etsu    Chemical Co., Ltd.);

-   triethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonly known    as 3-glycidoxypropyl triethoxysilane (KBE-403 from Shin-Etsu    Chemical Co., Ltd.);

-   ((triethoxysilyl)propyl)disulfide (Si-75 or Si-266 from Evonik);

-   ((trimethoxysilyl)propyl)disulfide;

-   diethoxy(propoxy)(3-thiocyanatopropyl)silane, commercially available    as SIT-7908.0 from Gelest;

-   2,2′-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-methylphenol)    (AO-80 from TCI Japan);

-   6,6′-methylenebis(2-(2-hydroxy-5-methylbenzyl)-4-methylphenol)    (4-PC);

-   bis(4-(2-phenylpropan-2-yl)phenyl)amine, commercially available as    Naugard-445 from Addivant;

-   pentaerythritol    tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox    1010 from BASF);

-   3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester    benzenepropanoic acid (Irganox 1076 from BASF); and

-   3,3′-[[1,1′-biphenyl]-4,4′-diylbis(methyleneoxymethylene)]bis[3-ethyl-oxetane

In the embodiments of the present invention, these components aregenerally dissolved in a solvent and prepared into a varnish form to beused. As a solvent, there may be used N-methyl-2-pyrrolidone (NMP),γ-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), dimethylsulfoxide(DMSO), diethyleneglycol dimethyl ether, diethyleneglycol diethylether,diethyleneglycol dibutylether, propyleneglycol monomethylether (PGME),dipropylene glycol monomethylether, propyleneglycol monomethyletheracetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methylethyl ketone (MEK), methyl amyl ketone (MAK), cyclohexanone,tetrahydrofuran, methyl-1,3-butyleneglycolacetate,1,3-butyleneglycol-3-monomethylether, methyl pyruvate, ethyl pyruvate,methyl-3-methoxypropionate or the like. They may be used solely or mixedby optionally selecting two or more kinds.

In one embodiment of the composition of this invention, the solvent usedin forming the composition is selected form the group consisting ofpropyleneglycol monomethylether acetate (PGMEA), gamma-butyrolactone(GBL) and N-methylpyrrolidone (NMP) and a mixture in any combinationthereof.

As mentioned above, some embodiments of the present invention encompassstructures, such as optoelectronic structures, which include at leastone self-imagable layer formed from a film of a polymer compositionembodiment in accordance with the present invention.

The aforementioned structure embodiments of the present invention arereadily formed by first casting or applying a polymer composition overan appropriate substrate to form a layer or a film thereof, then heatingthe substrate to an appropriate temperature for an appropriate time,where such time and temperature are sufficient to remove essentially allof the casting solvent of such composition. After such first heating,the layer is image-wise exposed to an appropriate wavelength of actinicradiation. As described hereinabove, the aforementioned image-wiseexposure causes the PAC contained in the exposed portions of the layerto undergo a chemical reaction to form a free acid that enhances thedissolution rate of such exposed portions to an aqueous base solution(generally a solution of tetramethylammonium hydroxide (TMAH)). In thismanner, such exposed portions are removed and unexposed portions remain.Next a second heating is performed to cause ring closure of the portionsof the polymer and/or cross-linking with the epoxy additive, if present,thus essentially “curing” the polymer of such unexposed portions to forman aforementioned structure embodiment of the present invention.

It should be noted again that the second heating step, post developmentbake/curing is performed for the imaged and developed layer. In thisstep of second heating, the thermal curing of the polymer layer can beachieved with the added additives, such as epoxies and/or othercrosslinking agents as described herein.

Accordingly, there is further provided a cured product obtained bycuring the composition of this invention as described herein. In afurther embodiment of this invention there is also provided anoptoelectronic or microelectronic device encompassing the cured productof this invention, which is having a dielectric constant of 3.2 or lessat 1 MHz.

The following examples, without being limiting in nature, illustratemethods for making composition embodiments in accordance with thepresent invention.

It should further be noted that the following examples are detaileddescriptions of methods of preparation and use of certaincompounds/monomers, polymers and compositions of the present invention.The detailed preparations fall within the scope of, and serve toexemplify, the more generally described methods of preparation set forthabove. The examples are presented for illustrative purposes only, andare not intended as a restriction on the scope of the invention.

EXAMPLES (GENERAL)

The following definitions have been used in the Examples that followunless otherwise indicated:

NBD: norbornadiene; MA: maleic anhydride; MI: maleimide; N-CyHexMI:N-cyclohexylmaleimide; N-PhMI: N-phenylmaleimide; NB: norbornene; NBTON:5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene;TrisP3M6C-2-201: a PAC of formula (VIo) in which Q is of formula (Va);TMPTGE: trimethylolpropane triglycidylether; VG3101L:2,2′-((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane);GE-36: triglycidyl ether of poly(oxypropylene)epoxide ether of glycerol;Heloxy 505: castor oil poly glycidyl ether; GT-401: an epoxycrosslinker; JER1032H60: an epoxy crosslinker; THETATO:1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione; TOTATO:1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione; Powderlink1174:1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione;N—BOC JD-2000; BY16-115: Silicone modified epoxy compound; PMDA:1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone; CXC 1614: acidcatalyst from King Industries Inc.; CXC 1761: thermal base catalyst fromKing Industries Inc.; WPBG-174:1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl cyclohexylcarbamate;KBM-403E: trimethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonlyknown as 3-glycidoxypropyl trimethoxysilane; FC-4432: afluoro-surfactant-2-propenoic acid,2-[methyl[(nonafluorobutyl)sulfonyl]amino]ethyl ester, telomer withmethyloxirane polymer with oxirane di-2-propenoate and methyloxiranepolymer with oxirane mono-propenoate; Cymel 1170:N2,N2,N4,N4,N6,N6-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine;THF: Tetrahydrofuran; DMAc: N, N-dimethylacetamide; DMSO:dimethylsulfoxide; NMP: N-methyl-2-pyrrolidone; GBL: γ-butyrolactone;GPC: high performance liquid chromatography; GPC: gel permeationchromatography; M_(w): weight average molecular weight; M_(n): numberaverage molecular weight; PDI: polydispersity index; pphr: parts perhundred resin; FT-IR: Fourier transform-infrared; NMR: nuclear magneticresonance; TGA: thermogravimetric analysis.

Polymers

The polymers used to form the photosensitive compositions of thisinvention are prepared generally in accordance with the well-knownliterature procedures. See for example, the U.S. Pat. No. 8,715,900,pertinent portions of which are incorporated herein by reference. Thefollowing examples are further provided to illustrate the preparation ofthe COMA and ROMA polymers as described herein.

Example 1 Terpolymer of NBD/MA/N-PhMI

Maleic anhydride (MA, 4.9 g, 50 mmol), N-phenyl maleimide (N-PhMI, 7.45g, 43 mmol) and 2,5-norbornadiene (NBD, 9.2 g, 100 mmol) were dissolvedin toluene (67 g) and charged to an appropriately sized reaction vesselhaving a nitrogen inlet/outlet, water-cooling condenser and a port for athermocouple. The solution was sparged with nitrogen for 10 min toremove oxygen and then heated to about 65° C. Lauryl peroxide (0.8 g, 2mmol) was then added and the mixture was allowed to stir at 65-70° C.for 5 hrs, after which the solution was cooled to room temperature. Thesolid polymer was separated out of the solution and washed with excessheptanes, filtered and dried in a vacuum oven at 80° C. for 20 hrs.Approximately 18 g (84% yield) of the NBD/N-PhMI/MA polymer was isolated(GPC (DMAc) M_(w)=52,350, M_(n)=15,400, PDI=3.4). ¹³C-NMRcharacterization of the polymer in deuterated DMSO showed peaks at 10-20ppm for the presence of cyclopropane structure and two peaks at about170-180 ppm for the presence of the carbonyl group of the cyclicanhydride structures from both MA and N-PhMI (i.e., repeat units offormulae (IIB) and (IIIA) respectively). FT-IR characterization of thepolymer showed peaks at 1860 cm⁻¹ and 1781 cm⁻¹ for the presence of thecarbonyl group of cyclic anhydride structure from MA and at 1712 cm⁻¹for the carbonyl group of cyclic anhydride structure from N-PhMI. Thecomposition of the polymer is estimated to be 42/30/28 of NBD/N-PhMI/MAbased on ¹H and ¹³C-NMR data. Based on the ‘H and’³C-NMR data it wasfurther determined that of the 42 mol % of the NBD repeat units 37 mol %are due to repeat units of formula (IA) and 5 mol % are due to repeatunits of formula (IB).

Example 2 Terpolymer of NBD/MA/MI

Maleic anhydride (MA, 10.3 g, 105 mmol), maleimide (MI, 4.4 g, 45 mmol)and 2,5-norbornadiene (NBD, 13.8 g, 150 mmol) were dissolved in toluene(69.2 g) and charged to an appropriately sized reaction vessel having anitrogen inlet/outlet, water-cooling condenser and a port for athermocouple. The solution was sparged with nitrogen for 10 min toremove oxygen and then heated to about 65° C. Lauryl peroxide (1.2 g, 3mmol) was then added and the mixture was allowed to stir at 65-70° C.for 5 hrs, after which the solution was cooled to room temperature. Thesolid polymer was separated out of the solution and washed with excessheptanes, filtered and dried in a vacuum oven at 80° C. for 20 hrs.Approximately 23.6 g (83% yield) of the NBD/MI/MA polymer was isolated(GPC (DMAc) M_(w)=43,200, M_(n)=19,000, PDI=2.27). ¹³C-NMRcharacterization of the polymer in deuterated DMSO showed peaks at 10-20ppm for the presence of cyclopropane structure and a peak at about 175ppm for the presence of carbonyl group of the cyclic anhydride structurefrom MA and a peak at about 180 ppm for carbonyl group of cyclicanhydride structure from MI. FT-IR characterization of the polymershowed peaks at 1859 cm⁻¹ and 1775 cm⁻¹ for the presence of the carbonylgroup of the cyclic anhydride structure from MA and at 1719 cm⁻¹ for thecarbonyl group of the cyclic imide structure from MI, i.e., respectivelyformulae (IIB) and (IIIA) as described herein. The composition of thepolymer is estimated to be 38/13/49 of NBD/MI/MA based on ¹³C-NMR data.

Example 3 Tetrapolymer of NBD/NBTON/N-PhMI/MA

Maleic anhydride (MA, 9.8 g, 100 mmol), N-PhMI maleimide (N-PHMI, 14.9g, 86 mmol), NBTON (13.6 g, 60 mmol) and 2,5-norbornadiene (NBD, 12.9 g,140 mmol) were dissolved in cyclopentanone (122.1 g) and charged to anappropriately sized reaction vessel having a nitrogen inlet/outlet,water-cooling condenser and a port for a thermocouple. The solution wassparged with nitrogen for 10 min to remove oxygen and then heated toabout 65° C. Lauryl peroxide (1.2 g, 3 mmol) was then added and themixture was allowed to stir at 65-70° C. for 5 hrs, after which thesolution was cooled to room temperature. Some solvent had evaporatedduring this time while cooling to room temperature. Toluene (75 g) andtetrahydrofuran (THF, 50 g) were added to obtain about 205 g of thepolymer solution. The polymer was precipitated from about 25 g of thispolymer solution by adding into excess heptanes, filtered and dried in avacuum oven at 80° C. for 20 hrs. Approximately 3.2 g (62% yield) of theNBD/NBTON/N-PhMI/MA polymer was isolated (GPC (DMAc) M_(w)=22,500,M_(n)=14,100, PDI=1.6). ¹³C-NMR characterization of the polymer indeuterated DMSO showed peaks at 10-20 ppm for the presence ofcyclopropane structure and peaks at about 170-180 ppm for the presenceof carbonyl groups of cyclic anhydride structure from MA and N-PhMI.Peaks at 125-150 ppm showed the presence of aromatic carbons fromN-PhMI. Three peaks at 68-76 ppm showed the presence of carbon from—CH₂O— groups from NBTON. FT-IR characterization of the polymer showedpeaks at 1859 cm⁻¹ and 1779 cm⁻¹ for the presence of the carbonyl groupsof cyclic anhydride structure from MA and at 1712 cm⁻¹ for the carbonylgroups cyclic anhydride structure from N-PhMI. The composition of thepolymer is estimated to be 33/10/33/24 of NBD/NBTON/N-PhMI/MA based on¹³C-NMR data.

Example 4 Terpolymer of NBD/N-CyHexMI/MA

Maleic anhydride (MA, 24.5 g, 250 mmol), N-Cyclohexyl maleimide(N-CyHexMI, 44.75 g, 250 mmol) and 2,5-norbornadiene (NBD, 46 g, 500mmol) were dissolved in cyclopentanone (238 g) and charged to anappropriately sized reaction vessel having a nitrogen inlet/outlet,water-cooling condenser and a port for a thermocouple. The solution wassparged with nitrogen for 10 min to remove oxygen and then heated toabout 65° C. Lauryl peroxide (1 g, 2.5 mmol) was then added and themixture was allowed to stir for 5 mins during which time the temperatureof the reaction mixture increased by about 3° C. Additional amounts oflauryl peroxide (1 g, 2.5 mmol) were added, the temperature of thereaction mixture increased by about 10° C. in about 9 minutes and themixture was allowed to stir at 65-70° C. for 5 hrs, after which thesolution was cooled to room temperature. About 320 g of the polymersolution was mixed with THF (50 g). The polymer was precipitated fromabout 10 g of this polymer solution by adding into excess heptanes,filtered and dried in a vacuum oven at 80° C. for 20 hrs. Approximately2.5 g (80% yield) of the NBD/N-CyHexMI/MA polymer was isolated (GPC(DMAc) M_(w)=37,300, M_(n)=14,550, PDI=2.6). FT-IR characterization ofthe polymer showed peaks at 1861 cm⁻¹ and 1778 cm⁻¹ for the presence ofthe carbonyl groups of the cyclic anhydride structure from MA and at1700 cm⁻¹ for the carbonyl groups of the cyclic imide structure fromN-CyHexMI. The composition of the polymer is estimated to be 50/23/27 ofNBD/N-CyHexMI/MA based on ¹³C-NMR data.

Example 5 Tetrapolymer of NBD/N-CyHexMI/MI/MA

Maleic anhydride (MA, 20.6 g, 210 mmol), N-CyHexMI (18.8 g, 105 mmol),MI (3.4 g, 35 mmol) and 2,5-norbornadiene (NBD, 32.2 g, 350 mmol) weredissolved in cyclopentanone (143 g) and charged to an appropriatelysized reaction vessel having a nitrogen inlet/outlet, water-coolingcondenser and a port for a thermocouple. The solution was sparged withnitrogen for 10 min to remove oxygen and then heated to about 65° C.Lauryl peroxide (2.1 g, 5.3 mmol) was then added and the mixture wasallowed to stir at 65-70° C. for 5 hrs, after which the solution wascooled to room temperature. About 220 g of the polymer solution wasmixed with THF (17 g). The polymer was precipitated from about 20 g ofthis polymer solution by adding into excess heptanes, filtered and driedin a vacuum oven at 80° C. for 20 hrs. Approximately 5.7 g (90% yield)of the NBD/N-CyHexMI/MI/MA polymer was isolated (GPC (DMAc)M_(w)=36,600, M_(n)=13,000, PDI=2.8). ¹³C-NMR characterization of thepolymer in deuterated DMSO showed peaks at 10-20 ppm for the presence ofcyclopropane structure and peaks at about 170-180 ppm for the presenceof carbonyl groups of the cyclic anhydride structure from MA, N-CyHexMIand N-HMI. FT-IR characterization of the polymer showed peaks at 1861cm⁻¹ and 1774 cm⁻¹ for the presence of the carbonyl groups of cyclicanhydride structure from MA, and 1696 cm⁻¹ for the carbonyl groupscyclic anhydride structure from N-CycHexMI and MI. The composition ofthe polymer is estimated to be 53% NBD and 47% of N-CyHexMI, MI and MAbased on ¹³C-NMR data.

Example 6 Tetrapolymer of NBD/N-CyHexMI/MI/MA

Maleic anhydride (MA, 26.5 g, 270 mmol), N-CyHexMI (34 g, 190 mmol), MI(3.9 g, 40 mmol) and 2,5-norbornadiene (NBD, 46 g, 500 mmol) weredissolved in cyclopentanone (228 g) and charged to an appropriatelysized reaction vessel having a nitrogen inlet/outlet, water-coolingcondenser and a port for a thermocouple. The solution was sparged withnitrogen for 10 min to remove oxygen and then heated to about 65° C.Lauryl peroxide (2 g, 5 mmol) added in two batches with a 5 minsinterval and the mixture was allowed to stir at 65-70° C. for 5 hrs,after which the solution was cooled to room temperature. The polymer wasprecipitated from about 25 g of this polymer solution by adding intoexcess heptanes, filtered and dried in a vacuum oven at 80° C. for 20hrs. Approximately 7.5 g (87% yield) of the NBD/N-CyHexMI/MI/MA polymerwas isolated (GPC (DMAc) M_(w)=42,550, M_(n)=16,600, PDI=2.6). ¹³C-NMRcharacterization of the polymer in deuterated DMSO showed peaks at 10-20ppm for the presence of cyclopropane structure and peaks at about170-180 ppm for the presence of carbonyl groups of cyclic anhydridestructure from MA, N-CyHexMI and N-HMI. FT-IR characterization of thepolymer showed peaks at 1860 cm⁻¹ and 1777 cm⁻¹ for the presence of thecarbonyl groups of cyclic anhydride structure from MA and at 1699 cm⁻¹for the carbonyl groups cyclic imide structure from N-CyHexMI and N-HMI.The composition of the polymer is estimated to be 47% NBD, 32% MA and20% N-CyHexMI and N-HMI based on ¹³C-NMR data.

Example 7 Tetrapolymer of NBD/N-PhMI/MI/MA

Maleic anhydride (MA, 13.7 g, 153 mmol), N-PhMI (20.9 g, 121 mmol), MI(6.8 g, 70 mmol) and 2,5-norbornadiene (NBD, 32.2 g, 350 mmol) weredissolved in cyclopentanone (113.5 g) and charged to an appropriatelysized reaction vessel having a nitrogen inlet/outlet, water-coolingcondenser and a port for a thermocouple. The solution was sparged withnitrogen for 10 min to remove oxygen and then heated to about 65° C.Lauryl peroxide (2.1 g, 5.3 mmol) added and the mixture was allowed tostir at 65-70° C. for 5 hrs, after which the solution was cooled to roomtemperature. THF (125 g) and toluene (100 g) added to the reactionmixture. The polymer was precipitated from about 30 g of this solutionby adding into excess heptanes, filtered and dried in a vacuum oven at60° C. for 24 hrs. Approximately 4.1 g (83% yield) of theNBD/N-CyHexMI/MI/MA polymer was isolated (GPC (DMAc) M_(w)=68,700,M_(n)=19,600, PDI=3.5). ¹³C-NMR characterization of the polymer indeuterated DMSO showed peaks at 10-20 ppm for the presence ofcyclopropane structure and peaks at about 175 ppm for the presence ofcarbonyl groups of cyclic anhydride structure from MA, N-CyHexMI and MI.FT-IR characterization of the polymer showed peaks at 1860 cm⁻¹ and 1778cm⁻¹ for the presence of the carbonyl groups of cyclic anhydridestructure from MA and at 1708 cm⁻¹ for the carbonyl groups cyclic imidestructure from N-PhMI and N-HMI.

ROMA Polymers

The following examples illustrate the preparation of a variety of ROMApolymers of this invention. Various other ROMA polymers can besynthesized using similar procedures and various other COMA polymers andusing appropriate alcohols as needed.

Example 8

Terpolymer of NBD/N-PhMI/ROMA-MeOH

The polymer from Example 1 (NBD/N-PhMI/MA terpolymer, 12 g), THF (75 g),methanol (25 g) and 25% sodium methoxide in methanol (5.5 g) were mixedin an appropriately sized reaction vessel having a nitrogeninlet/outlet, water-cooling condenser and a port for a thermocouple. Themixture was heated to 60° C. for 6 hrs while stirring under nitrogenatmosphere. Concentrated hydrochloric acid (6 g) was added to thereaction mixture slowly and heating continued for 2 hrs. The solutionwas cooled to room temperature and toluene (30 g), THF (20 g) anddistilled water (30 g) added while stirring. The stirring stopped andthe solution was allowed to phase separate. The bottom aqueous layer wasremoved. Concentrated hydrochloric acid (6 g) was again added to thepolymer solution and stirred for about 15 minutes. The polymer solutionwas washed five times using 50 g of distilled water at each step. About20 g of THF added to the solution at each step to facilitate phaseseparation. The polymer was precipitated by adding the solution toexcess heptanes (200 g), filtered, washed with heptanes (200 g) anddried in a vacuum oven at 60° C. for 20 hrs. Approximately 11 g (84%yield) of the NBD/N-PhMI/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=61,950, M_(n)=19,750, PDI=3.14). FT-IR characterization of thepolymer showed no peaks at 1860 cm⁻¹ and 1781 cm⁻¹ for the presence ofthe carbonyl groups of cyclic anhydride structure from MA. A peak at1713 cm⁻¹ indicated the presence of carbonyl groups of carboxylic acid,its ester and the carbonyl of maleimide of N-PhMI. A broad peak at2400-3600 cm⁻¹ indicated the presence of hydroxyl group of a carboxylicacid.

Example 9

Terpolymer of NBD/MI/ROMA-MeOH

The polymer from Example 2 (NBD/N-HMI/MA, 15 g), cyclopentanone (45 g),THF (20 g), methanol (15 g) and 25% sodium methoxide in methanol (11.7g) were mixed in an appropriately sized reaction vessel having anitrogen inlet/outlet, water-cooling condenser and a port for athermocouple. The mixture was heated to 60° C. for 6 hrs while stirringunder nitrogen atmosphere. Concentrated hydrochloric acid (11 g) wasadded to the reaction mixture slowly and heating continued for 2 hrs.The solution was cooled to room temperature and distilled water (30 g)was added while stirring. The stirring stopped and the solution wasallowed to phase separate. The bottom aqueous layer removed.Concentrated hydrochloric acid (11 g) added to the polymer solution andstirred for about 15 minutes. The polymer solution was washed five timesusing 50 g of distilled water at each step. About 20 g of THF added tothe solution at each step to facilitate phase separation. The polymerwas precipitated by adding the solution to excess heptanes (200 g),filtered, washed with heptanes (200 g) and dried in a vacuum oven at 60°C. for 20 hrs. Approximately 13.8 g (79% yield) of the NBD/MI/ROMA-MeOHpolymer was isolated (GPC (DMAc) M_(w)=53,200, M_(n)=27,150, PDI=1.96).FT-IR characterization of the polymer showed no peaks at 1859 cm⁻¹ and1775 cm⁻¹ for the presence of the carbonyl groups of cyclic anhydridestructure from MA. A peak at 1719 cm⁻¹ indicated the presence ofcarbonyl groups of carboxylic acid, its ester and carbonyl groups of MI.A broad peak at 2300-3600 cm⁻¹ indicated the presence of hydroxyl groupof a carboxylic acid. The composition of the polymer is estimated to be49/11/40 NBD/MI/ROMA-MeOH based on ¹H-NMR and ¹³C-NMR data. The NMR datafurther showed that the composition of NBD repeat units were as follows:repeat units of formula (IA)—46 mol %; repeat units of formula (IB)—3mol %.

Example 10

-   -   where TON=CH₂OCH₂CH₂OCH₂CH₂OCH₃

Tetrapolymer of NBD/NBTON/N-PhMI/ROMA-MeOH

The polymer solution from Example 3 (NBD/NBTON/N-PhMI/MA, 175 g) and 25%sodium methoxide in methanol (20 g) were mixed in an appropriately sizedreaction vessel having a nitrogen inlet/outlet, water-cooling condenserand a port for a thermocouple. The mixture was heated to 60° C. for 6hrs while stirring under nitrogen atmosphere. Concentrated hydrochloricacid (20 g) was added to the reaction mixture slowly and heatingcontinued for 2 hrs. The solution was cooled to room temperature anddistilled water (100 g) was added while stirring. The stirring wasstopped and the solution was allowed to phase separate. The bottomaqueous layer was removed. The polymer solution was washed five timesusing 100 g of distilled water at each step. About 50 g of THF added tothe solution at each step to facilitate phase separation. The polymerwas precipitated by adding the solution to excess heptanes (2 L),filtered, washed with heptanes (1 L) and dried in a vacuum oven at 60°C. for 20 hrs. Approximately 23.5 g (51% yield) of theNBD/NBTON/N-PhMI/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=18,950, M_(n)=12.150 PDI=1.56). FT-IR characterization of thepolymer showed no peaks at 1859 cm⁻¹ and 1779 cm⁻¹ for the presence ofthe carbonyl groups of cyclic anhydride structure from MA. A peak at1713 cm⁻¹ indicated the presence of carbonyl groups of carboxylic acid,its ester and N-PhMI. A broad peak at 2300-3600 cm⁻¹ indicated thepresence of hydroxyl group of a carboxylic acid.

Example 11

Terpolymer of NBD/N-CyHexMI/ROMA-MeOH

The polymer solution from example 4 (NBD/N-CyHexMI/MA, 320 g) andtoluene (125 g) was transferred to an appropriately sized reactionvessel having a nitrogen inlet/outlet, water-cooling condenser and aport for a thermocouple, and methanol (50 g) and 25% sodium methoxide inmethanol (50 g) were mixed and transferred to the reaction vessel. Themixture was heated to 60° C. for 6 hrs while stirring under nitrogenatmosphere. Concentrated hydrochloric acid (50 g) was added to thereaction mixture slowly and heating continued for 2 hrs. The solutionwas cooled to room temperature and distilled water (250 g) was addedwhile stirring. The stirring stopped and the solution was allowed tophase separate. The bottom aqueous layer was removed. The polymersolution was washed five times using 250 g of distilled water at eachstep. About 50 g of THF added to the solution at each step to facilitatephase separation. The polymer was precipitated by adding the solution toexcess heptanes (2 L), filtered, washed with heptanes (1 L) and dried ina vacuum oven at 60° C. for 20 hrs. Approximately 80 g (77% yield) ofthe NBD/N-CyHexMI/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=42,750, M_(n)=16,400, PDI=2.6). FT-IR characterization of thepolymer showed no peaks at 1861 cm⁻¹ and 1778 cm⁻¹ for the presence ofthe carbonyl groups of cyclic anhydride structure from MA. A peak at1736 cm⁻¹ indicated the presence of carbonyl groups of carboxylic acid,its ester and a peak at 1700 cm⁻¹ indicated the presence of carbonylpeaks of N-CyHexMI. A broad peak at 2500-3600 cm⁻¹ indicated thepresence of hydroxyl group of a carboxylic acid.

Example 12

Tetrapolymer of NBD/N-CyHexMI/MI/ROMA-MeOH

The polymer solution from Example 5 (NBD/N-CyHexMI/MI/MA 220 g), THF(150 g), methanol (50 g) and 25% sodium methoxide in methanol (40 g)were mixed in an appropriately sized reaction vessel having a nitrogeninlet/outlet, water-cooling condenser and a port for a thermocouple. Themixture was heated to 60° C. for 6 hrs while stirring under nitrogenatmosphere. Concentrated hydrochloric acid (42 g) was added to thereaction mixture slowly and heating continued for 2 hrs. The solutionwas cooled to room temperature. Toluene (100 g) and distilled water (250g) were then added while stirring. The stirring stopped and the solutionwas allowed to phase separate. The bottom aqueous layer was removed. Thepolymer solution was washed five times using 250 g of distilled water ateach step. About 40 g of THF added to the solution at each step tofacilitate phase separation. The polymer was precipitated by adding thesolution to excess heptanes (1 L), filtered, washed with heptanes anddried in a vacuum oven at 60° C. for 20 hrs. Approximately 56 g (74%yield) of the NBD/N-CyHexMI/MI/ROMA-MeOH polymer was isolated (GPC(DMAc) M_(w)=44,200, M_(n)=16,350, PDI=2.7). FT-IR characterization ofthe polymer showed no peaks at 1861 cm⁻¹ and 1774 cm⁻¹ for the presenceof the carbonyl groups of cyclic anhydride structure from MA. Peak at1699 cm⁻¹ indicated the presence of carbonyl groups of carboxylic acid,its ester, MI and N-CyHexMI. A broad peak at 2300-3600 cm⁻¹ indicatedthe presence of hydroxyl group of a carboxylic acid.

Example 13 Tetrapolymer of NBD/N-CyHexMI/MI/ROMA-MeOH

The polymer solution from Example 6 (NBD/N-CyHexMI/N-HMI/MA, 200 g) wastransferred to an appropriately sized reaction vessel having a nitrogeninlet/outlet, water-cooling condenser and a port for a thermocouple andtoluene (75 g) was added. Methanol (37 g) and 25% sodium methoxide inmethanol (37 g) were mixed and added to the reaction vessel. The mixturewas heated to 60° C. for 6 hrs while stirring under nitrogen atmosphereand allowed to cool to the ambient temperature. Concentratedhydrochloric acid (40 g) was added to the reaction mixture slowly andheating continued for 2 hrs. The solution was cooled to room temperatureand distilled water (200 g) was added while stirring. The stirring wasstopped and the solution was allowed to phase separate. The bottomaqueous layer removed. The polymer solution was washed five times using200 g of distilled water at each step. About 50 g of THF added to thesolution at each step to facilitate phase separation. The polymer wasprecipitated by adding the solution to excess heptanes (1 L), filtered,washed with heptanes and dried in a vacuum oven at 60° C. for 20 hrs.Approximately 49.6 g (71% yield) of the NBD/N-CyHexMI/MI/ROMA-MeOHpolymer was isolated (GPC (DMAc) M_(w)=48,256, M_(n)=18,993, PDI=2.54).FT-IR characterization of the polymer showed no peaks at 1861 cm⁻¹ and1774 cm⁻¹ for the presence of the carbonyl groups of cyclic anhydridestructure from MA. Peaks at 1735 cm⁻¹ and 1697 cm⁻¹ indicated thepresence of carbonyl groups of carboxylic acid, its ester, MI, andN-CyHexMI. A broad peak at 2300-3600 cm⁻¹ indicated the presence ofhydroxyl group of a carboxylic acid.

Example 14 Tetrapolymer of NBD/N-PhMI/MI/ROMA-MeOH

The polymer solution from Example 7 (NBD/N-PhMI/MI/MA, 415 g) wastransferred to an appropriately sized reaction vessel having a nitrogeninlet/outlet, water-cooling condenser and a port for a thermocouple.Methanol (30 g) and 25% sodium methoxide in methanol (30 g) were mixedand added to the reaction vessel. The mixture was heated to 60° C. for 6hrs while stirring under nitrogen atmosphere and allowed to cool to theambient temperature. Concentrated hydrochloric acid (36 g) was added tothe reaction mixture slowly and heating continued for 2 hrs. Thesolution was cooled to room temperature and distilled water (200 g) wasadded while stirring. The stirring stopped and the solution was allowedto phase separate. The bottom aqueous layer was removed. The polymersolution was washed five times using 200 g of distilled water at eachstep. About 50 g of THF added to the solution at each step to facilitatephase separation. The polymer was precipitated by adding the solution toexcess heptanes (2.5 L), filtered, washed with heptanes and dried in avacuum oven at 60° C. for 24 hrs. Approximately 57.5 g (80% yield) ofthe NBD/N-PhMI/MI/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=73,200, M_(n)=20,850, PDI=3.5). FT-IR characterization of thepolymer showed no peaks at 1861 cm⁻¹ and 1774 cm⁻¹ for the presence ofthe carbonyl groups of cyclic anhydride structure from MA. Peaks at 1710cm⁻¹ indicated the presence of carbonyl groups of carboxylic acid, itsester, MI, and N-PhMI. A broad peak at 2300-3600 cm⁻¹ indicated thepresence of hydroxyl group of a carboxylic acid.

The following polymers were prepared to form comparative compositions inorder to show superior properties of the polymers of their invention andthe compositions derived therefrom.

Comparative Example 1 Copolymer of NB/MA

Maleic anhydride (14.7 g, 150 mmol) and norbornene (14.1 g, 150 mmol)were dissolved in toluene (70 g) and charged to an appropriately sizedreaction vessel having a nitrogen inlet/outlet, water-cooling condenserand a port for a thermocouple. The solution was sparged with nitrogenfor 10 min to remove oxygen and then heated to about 65° C. Laurylperoxide (1.2 g, 3 mmol) was added and the mixture was allowed to stirat 65-70° C. for 5 hrs, after which the solution was cooled to roomtemperature. The solid polymer was separated out of the solution andwashed with excess heptanes, filtered and dried in a vacuum oven at 80°C. for 20 hrs. Approximately 16.4 g (57% yield) of the NB/MA polymer wasisolated (GPC (DMAc) M_(w)=21,350, M_(n)=13,550, PDI=1.6). ¹³C-NMRcharacterization of the polymer in deuterated DMSO showed no peaks at10-20 ppm for the presence of cyclopropane structures. A peak at about175 ppm for the presence of the carbonyl groups of cyclic anhydridestructure from MA was observed. FT-IR characterization of the polymershowed peaks at 1853 cm⁻¹ and 1778 cm⁻¹ for the presence of the carbonylgroups of cyclic anhydride structure from MA. The composition of thepolymer is estimated to be 43/57 of NB/MA based on ¹³C-NMR data.

Comparative Example 2

Copolymer of NB/ROMA-MeOH

The polymer from Comparative Example 1 (NBD/MA, 12 g), THF (20 g),toluene (30 g), methanol (15 g) and 25% sodium methoxide in methanol(13.1 g) were mixed in an appropriately sized reaction vessel having anitrogen inlet/outlet, water-cooling condenser and a port for athermocouple. The mixture was heated to 60° C. for 6 hrs while stirringunder nitrogen atmosphere. Concentrated hydrochloric acid (13 g) wasadded to the reaction mixture slowly and heating continued for 2 hrs.The solution was cooled to room temperature. THF (20 g) and distilledwater (30 g) were added while stirring. The stirring stopped and thesolution was allowed to phase separate. The bottom aqueous layerremoved. Concentrated hydrochloric acid (13 g) added to the polymersolution and stirred for about 15 minutes. The polymer solution waswashed five times using 50 g of distilled water at each step. About 20 gof THF added to the solution at each step to facilitate phaseseparation. The polymer was precipitated by adding the solution toexcess heptanes (200 g), filtered, washed with heptanes (200 g) anddried in a vacuum oven at 60° C. for 20 hrs. Approximately 10.9 g (75%yield) of the NB/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=25,100, M_(n)=16,800, PDI=1.5). FT-IR characterization of thepolymer showed only minor peaks at 1853 cm⁻¹ and 1778 cm⁻¹ for thepresence of the carbonyl groups of cyclic anhydride structure from MA. Apeak at 1727 cm⁻¹ indicated the presence of carbonyl groups ofcarboxylic acid and its ester. A broad peak at 2300-3600 cm⁻¹ indicatedthe presence of hydroxyl group of a carboxylic acid.

Comparative Example 3 Copolymer of NBD/MA

Maleic anhydride (12.25 g, 125 mmol) and 2,5-norbornadiene (11.5 g, 125mmol) were dissolved in toluene (74.2 g) and charged to an appropriatelysized reaction vessel having a nitrogen inlet/outlet, water-coolingcondenser and a port for a thermocouple. The solution was sparged withnitrogen for 10 min to remove oxygen and then heated to about 65° C.Lauryl peroxide (1 g, 2.5 mmol) was added and the mixture was allowed tostir at 65-70° C. for 5.0 hrs, after which the solution was cooled toroom temperature. The solid polymer was separated out of the solutionand washed with excess heptanes, filtered and dried in a vacuum oven at80° C. for 20 hrs. Approximately 19 g (80% yield) of the NBD/MA polymerwas isolated (GPC (DMAc) M_(w)=75,000, M_(n)=21,600, PDI=3.5). ¹³C-NMRcharacterization of the polymer in deuterated DMSO showed peaks at 10-20ppm for the presence of cyclopropane structures and at about 175 ppm forthe presence of the carbonyl groups of cyclic anhydride structure fromMA. FT-IR characterization of the polymer showed peaks at 1860 cm⁻¹ and1782 cm⁻¹ for the presence of the carbonyl groups of cyclic anhydridestructure from MA. The composition of the polymer is estimated to be51/49 of NBD/MA based on ¹³C-NMR data. The NMR data further showed thatthe composition of NBD repeat units were as follows: repeat units offormula (IA)—47 mol %; repeat units of formula (IB)—4 mol %.

Comparative Example 4

Copolymer of NBD/ROMA-MeOH

The polymer from Comparative Example 3 (NBD/MA, 12 g), THF (75 g),methanol (25 g) and 25% sodium methoxide in methanol (13.4 g) were mixedin an appropriately sized reaction vessel having a nitrogeninlet/outlet, water-cooling condenser and a port for a thermocouple. Themixture was heated to 60° C. for 6 hrs while stirring under nitrogenatmosphere. Concentrated hydrochloric acid (13 g) was added to thereaction mixture slowly and heating continued for 2 hrs. The solutionwas cooled to room temperature and toluene (30 g), THF (20 g) anddistilled water (30 g) were added while stirring. The stirring stoppedand the solution was allowed to phase separate. The bottom aqueous layerremoved. Concentrated hydrochloric acid (13 g) was again added to thepolymer solution and stirred for about 15 minutes. The polymer solutionwas washed five times using 50 g of distilled water at each step. About20 g of THF added to the solution at each step to facilitate phaseseparation. The polymer was precipitated by adding the solution toexcess heptanes (200 g), filtered, washed with heptanes (200 g) anddried in a vacuum oven at 60° C. for 20 hrs. Approximately 11 g (75%yield) of the NBD/ROMA-MeOH polymer was isolated (GPC (DMAc)M_(w)=96,500, M_(n)=29,250, PDI=3.3). FT-IR characterization of thepolymer showed no peaks at 1860 cm⁻¹ and 1782 cm⁻¹ for the presence ofthe carbonyl groups of cyclic anhydride structure from MA. A peak at1735 cm⁻¹ indicated the presence of carbonyl groups of carboxylic acidand its ester. A broad peak at 2300-3600 cm⁻¹ indicated the presence ofhydroxyl group of a carboxylic acid.

Photoimagable Compositions

The following examples illustrate formation of the various compositionsof this invention containing a polymer, PAC and a variety of othercomponents/additives as described herein.

Example 15

A fully ring opened NBD/N-PhMI/ROMA-MeOH terpolymer of Example 8 (100parts) was dissolved in GBL (500 parts) having the specific amounts ofadditives, expressed as parts per hundred resin (phr): TrisP3M6C-2-201(25 phr) as a photo-active compound, TMPTGE (40 phr) as an epoxidecrosslinker, KBM-403E (5 phr) as an adhesion promoter and FC-4432 (0.3phr) as a surface leveling agent were mixed in an appropriately sizedamber HDPE bottle. The mixture was rolled for 18 hours to produce ahomogeneous solution. Particle contamination was removed by filteringthe polymer solution through a 0.45 μm pore polytetrafluoroethylene(PTFE) disc filter, the filtered polymer solution was collected in a lowparticle HDPE amber bottle and the resulting solution stored at 5° C.

Example 16

A fully ring opened NBD/MI/ROMA-MeOH terpolymer of Example 9 (100 parts)was dissolved in NMP (200 parts) having the specific amounts ofadditives, expressed as parts per hundred resin (phr): TrisP3M6C-2-201(25 phr) as a photo-active compound, TMPTGE (40 phr) as an epoxidecrosslinker, KBM-403E (5 phr) as an adhesion promoter and FC-4432 (0.3phr) as a surface leveling agent were mixed in an appropriately sizedamber HDPE bottle. The mixture was rolled for 18 hours to produce ahomogeneous solution. Particle contamination was removed by filteringthe polymer solution through a 0.45 μm pore polytetrafluoroethylene(PTFE) disc filter, the filtered polymer solution was collected in a lowparticle HDPE amber bottle and the resulting solution stored at 5° C.

Example 17

A fully ring opened NBD/N-CyHexMI/MI/ROMA-MeOH tetrapolymer of Example12 (100 parts) was dissolved in GBL (200 parts) and NMP (30 parts)having the specific amounts of additives, expressed as parts per hundredresin (phr): TrisP3M6C-2-201 (25 phr) as a photo-active compound,VG3101L (30 phr) and GE-36 (25 phr) as epoxide crosslinkers, KBM-403E (5phr) as an adhesion promoter, CXC 1761 (0.3 phr) as a thermal basecatalyst and FC-4432 (0.3 phr) as a surface leveling agent were mixed inan appropriately sized amber HDPE bottle. The mixture was rolled for 18hours to produce a homogeneous solution. Particle contamination wasremoved by filtering the polymer solution through a 0.45 μm porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and theresulting solution stored at 5° C.

Example 18

A fully ring opened NBD/N-CyHexMI/MI/ROMA-MeOH tetrapolymer of Example13 (100 parts) was dissolved in GBL (200 parts) and NMP (30 parts)having the specific amounts of additives, expressed as parts per hundredresin (phr): TrisP3M6C-2-201 (27.5 phr) as a photo-active compound,VG3101L (30 phr) and GE-36 (30 phr) as epoxide crosslinkers, KBM-403E (5phr) as an adhesion promoter, CXC 1761 (0.3 phr) as a thermal basecatalyst and FC-4432 (0.3 phr) as a surface leveling agent were mixed inan appropriately sized amber HDPE bottle. The mixture was rolled for 18hours to produce a homogeneous solution. Particle contamination wasremoved by filtering the polymer solution through a 0.45 m porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and theresulting solution stored at 5° C.

Example 19

A fully ring opened NBD/N-CyHexMI/MI/ROMA-MeOH tetrapolymer of Example13 (100 parts) was dissolved in GBL (200 parts) and NMP (30 parts)having the specific amounts of additives, expressed as parts per hundredresin (phr): TrisP3M6C-2-201 (27.5 phr) as a photo-active compound,VG3101L (30 phr), GT-401 (10 phr) and GE-36 (30 phr) as epoxidecrosslinkers, KBM-403E (5 phr) as an adhesion promoter, CXC 1761 (0.3phr) as a thermal base catalyst and FC-4432 (0.3 phr) as a surfaceleveling agent were mixed in an appropriately sized amber HDPE bottle.The mixture was rolled for 18 hours to produce a homogeneous solution.Particle contamination was removed by filtering the polymer solutionthrough a 0.45 μm pore polytetrafluoroethylene (PTFE) disc filter, thefiltered polymer solution was collected in a low particle HDPE amberbottle and the resulting solution stored at 5° C.

Example 20

A fully ring opened NBD/N-CyHexMI/MI/ROMA tetrapolymer of Example 13(100 parts) was dissolved in GBL (200 parts) and NMP (30 parts) havingthe specific amounts of additives, expressed as parts per hundred resin(phr): TrisP3M6C-2-201 (27.5 phr) as a photo-active compound, VG3101L(30 phr), GE-36 (30 phr), JER1032H60 (10 phr) and GT-401 (10 phr) asepoxide crosslinkers, KBM-403E (5 phr) as an adhesion promoter, CXC 1761(0.3 phr) as a thermal base catalyst and FC-4432 (0.3 phr) as a surfaceleveling agent were mixed in an appropriately sized amber HDPE bottle.The mixture was rolled for 18 hours to produce a homogeneous solution.Particle contamination was removed by filtering the polymer solutionthrough a 0.45 μm pore polytetrafluoroethylene (PTFE) disc filter, thefiltered polymer solution was collected in a low particle HDPE amberbottle and the resulting solution stored at 5° C.

Example 21

A fully ring opened NBD/N-PhMI/ROMA terpolymer of Example 8 (100 parts)was dissolved in GBL (250 parts) having the specific amounts ofadditives, expressed as parts per hundred parts resin (phr):TrisP3M6C-2-201 (25 phr) as a photo-active compound, Powderlink 1174 (40phr) and Heloxy 505 (20 phr) as epoxide crosslinkers, KBM-403E (5 phr)as an adhesion promoter, CXC 1761 (0.3 phr) as a thermal base catalystand FC-4432 (0.3 phr) as a surface leveling agent were mixed in anappropriately sized amber HDPE bottle. The mixture was rolled for 18hours to produce a homogeneous solution. Particle contamination wasremoved by filtering the polymer solution through a 0.45 μm porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and theresulting solution stored at 5° C.

Example 22

A fully ring opened NBD/N-PhMI/ROMA terpolymer of Example 14 (100 parts)was dissolved in GBL (250 parts) having the specific amounts ofadditives, expressed as parts per hundred parts resin (phr):TrisP3M6C-2-201 (25 phr) as a photo-active compound, VG3101L (40 phr) asan epoxide cross linker, KBM-403E (5 phr) as an adhesion promoter andFC-4432 (0.3 phr) as a surface leveling agent were mixed in anappropriately sized amber HDPE bottle. The mixture was rolled for 18hours to produce a homogeneous solution. Particle contamination wasremoved by filtering the polymer solution through a 0.45 μm porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and theresulting solution stored at 5° C.

Comparative Example 5

A fully ring opened NB/ROMA-MeOH copolymer of Comparative Example 2 (100parts) was dissolved in GBL (200 parts) having the specific amounts ofadditives, expressed as parts per hundred resin (phr): TrisP3M6C-2-201(25 phr) as a photo-active compound, TMPTGE (40 phr) as an epoxide crosslinker, KBM-403E (5 phr) as an adhesion promoter and FC-4432 (0.3 phr)as a surface leveling agent were mixed in an appropriately sized amberHDPE bottle. The mixture was rolled for 18 hours to produce ahomogeneous solution. Particle contamination was removed by filteringthe polymer solution through a 0.45 μm pore polytetrafluoroethylene(PTFE) disc filter, the filtered polymer solution was collected in a lowparticle HDPE amber bottle and the resulting solution stored at 5° C.

Comparative Example 6

A fully ring opened NBD/ROMA-MeOH copolymer of Comparative Example 4(100 parts) was dissolved in GBL (500 parts) having the specific amountsof additives, expressed as parts per hundred resin (phr):TrisP3M6C-2-201 (25 phr) as a photo-active compound, TMPTGE (40 phr) asan epoxide crosslinker, KBM-403E (5 phr) as an adhesion promoter andFC-4432 (0.3 phr) as a surface leveling agent were mixed in anappropriately sized amber HDPE bottle. The mixture was rolled for 18hours to produce a homogeneous solution. Particle contamination wasremoved by filtering the polymer solution through a 0.45 μm porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and theresulting solution stored at 5° C.

Example 23 FT-IR Measurements

The composition as obtained in Comparative Example 6 was spin coated ona 5-inch bare silicon wafer at a spin speed of 600 rpm for 30 seconds.The coated film was post apply baked (PAB) at 120° C. on a hot plate for3 minutes to obtain a film thickness of 15.1 μm. This film was hardbaked at 200° C. for 1 hr in an oven kept under nitrogen atmosphere. Thefilm thickness dropped to 14.2 μm after the hard bake. The cured film onthe bare silicon wafer was diced into about 10 mm wide strips. The 10 mmwide film strips were lifted out of the wafer by immersing in 1 wt. %hydrogen fluoride solution and allowed to dry in air. The FT-IR of asample of the film was recorded and shown in top of FIG. 1, designatedas “Comparative Example 6”.

Likewise the composition as obtained in Comparative Example 5 was spincoated on a 5-inch bare silicon wafer at a spin speed of 300 rpm for 30seconds. The coated film was post apply baked (PAB) at 120° C. on a hotplate for 3 minutes to obtain a film thickness of 21.3 μm. This film washard baked at 200° C. for 1 hr in an oven kept under nitrogenatmosphere. The film thickness dropped to 19.7 μm after the hard bake.The cured film on the bare silicon wafer was diced into about 10 mm widestrips. The 10 mm wide film strips were lifted out of the wafer byimmersing in 1 wt. % hydrogen fluoride solution and allowed to dry inair. The FT-IR of a sample of the film was recorded and also shown inbottom of FIG. 1, designated as “Comparative Example 5.” Both of theseIP spectra as shown in FIG. 1 show peaks at about 1860 cm⁻¹ and 1780cm⁻¹ for the presence of cyclic anhydride and a peak at 1732 cm⁻¹ forthe presence of carboxylic acid and a carboxylic acid ester. Thecarboxylic acid ester peak is representative of the methyl ester of thecarboxylic acid of ROMA polymer examples and the ester formed by thereaction of carboxylic acid of NBD/ROMA or NB/ROMA with the epoxidecross linker, TMPTGE.

It is shown in top IR spectrum in FIG. 1 that the height of the peak atabout 1780 cm⁻¹ of the cured film of Comparative Example 6 containingNBD/ROMA is only about half of the height of the peak at 1732 cm⁻¹suggesting lower degree of ring closing compared to cross linking withTMPTGE. It is also shown in bottom IR spectrum in FIG. 1 that the heightof the peak at about 1780 cm⁻¹ of the cured film of the composition fromthe Comparative Example 5 containing NB/ROMA is higher than the heightof the peak at 1732 cm⁻¹ suggesting higher degree of ring closingcompared to cross linking with TMPTGE.

This Example clearly demonstrates that the compositions containing theNBD polymers do not form as much ring-closed structures (i.e., repeatunits of formula (IIB)) and therefore are more highly crosslinked, thusfeaturing improved thermomechanical properties as further manifested bythe following Examples.

Example 24 Glass Transition (T_(g)) and Coefficient of Thermal Expansion(CTE) Measurements

The compositions from Examples 15, 16 and Comparative Examples 5 and 6were spin coated on 5-inch bare silicon wafers and post apply baked(PAB) at 120° C. on a hot plate for 3 minutes. These films were hardbaked at 200° C. for 1 hr in an oven kept under nitrogen atmosphere. Thecured films on the bare silicon wafer were diced into about 10 mm widestrips. The 10 mm wide film strips were lifted out of the wafer byimmersing in 1 wt. % hydrogen fluoride solution and allowed to dry inair. The glass transition temperatures and coefficients of thermalexpansion (CTE) were measured by thermomechanical analysis (TMA)instrument at 10° C./min temperature ramp and 0.02N force. Glasstransition temperatures (T_(g)) were also measured by dynamic mechanicalanalysis instrument (DMA). The CTE measured at about 60-120° C. rangeand glass transition temperatures as T_(α) and T_(β) are summarized inTable 1. In some instances only one glass transition were observed. Itis clear from the data presented in Table 1 that the polymers (i.e.,NBD/maleimide/ROMA polymers) of this invention generally exhibit higherglass transition temperatures than the polymers of the comparativeexamples (i.e., both NB/ROMA polymer and NBD/ROMA polymer).

FIG. 2 shows the thermograms of each of these samples. It is clear fromthis data that the composition of Comparative Example 5 shows lowerglass transition than all other samples. All of NBD containingcompositions exhibit higher T_(g) as also shown in FIG. 2, and the dataas summarized in Table 1.

TABLE 1 CTE T_(α) (° C.) T_(β) (° C.) T_(g) (° C.) Example (ppm K⁻¹) TMATMA DMA 15 67 343 210 351 16 72 370 — 353 Comparative 5 79 314 220 270Comparative 6 80 >350 — 341

Example 25 Thermomechanical Properties

The compositions from each of Examples 18 to 21 were spin coated on5-inch bare silicon wafers and post apply baked (PAB) at 110-120° C. ona hot plate for 3 minutes. These films were hard baked at 200° C. for 2hrs in an oven kept under nitrogen atmosphere. The cured films on thebare silicon wafer were diced into about 4.5 mm, 6.5 mm, 10 mm and 15 mmwide strips. The film strips were lifted out of the wafer by immersingin 1 wt. % hydrogen fluoride solution and allowed to dry in air. Theserectangular films were cut into 20 mm length and thermomechanicalproperties were measured by Instron and TMA.

Likewise the compositions from each of Examples 18 to 21 were spincoated on 5-inch bare silicon wafers and post apply baked (PAB) at 105°C. on a hot plate for 3 minutes. The films were then exposed using apatterned mask to a broad band Hg-vapor light source (at 365 nm using aband pass filter) at an exposure dose of 750-1000 mJ/cm². Thedevelopment of these exposed films by 2.4 wt. % TMAH retained rectanglesof 4.5 mm, 6.5 mm and 15 mm film strips. These films were hard baked at200° C. for 2 hrs in an oven kept under nitrogen atmosphere. The filmstrips were lifted out of the wafer by immersing in 1 wt. % hydrogenfluoride solution and allowed to dry in air. These rectangular filmswere cut into 20 mm length and mechanical properties were measured byInstron, thermomechanical analysis (TMA), after a stress relief bake of10° C. to 250° C. at 5° C./min temperature ramp followed by cooling to10° C., and dynamic mechanical analysis (DMA). The average mechanicalproperties of each of these Examples are summarized in Table 2.

TABLE 2 Tensile Tensile T_(α) T_(g) Compo- Modulus Strength ETB CTE (°C.) (° C.) sition (GPa) (MPa) (%) (ppmK⁻¹) (TMA) (DMA) 18 2.0 ± 0.3 68 ±13 18 ± 13 108 300 278 19 1.8 ± 0.3 67 ± 16 22 ± 16 108 >300 284 20 1.9± 0.1 72 ± 9  21 ± 17 111 340 274 21 3.4 ± 5  92 ± 10 4 ± 1 −34 >350 —

Example 26

The composition of Example 17 was spin coated at a spin speed of 1300rpm for 30 seconds on a 4-inch thermal oxide silicon wafer. The coatedfilm was post apply baked (PAB) at 100° C. on a hot plate for 3 minutesto obtain a film thickness of 8.52 m. The film was then exposed using acombination of a patterned mask and a variable density mask to a broadband Hg-vapor light source (at 365 nm using a band pass filter). Thefilm was developed for 10 seconds with 2.4 wt. % TMAH in a puddle,rinsed with distilled water and dried using a stream of nitrogen. Thefilm thicknesses (FT) after development was 6.14 μm. The unexposed filmthickness loss or dark field loss (DFL) of 28% was calculated based onfilm thicknesses before and after development. The film was cured at200° C. for 2 hours in an oven under nitrogen atmosphere. FIG. 3 showsthe laser microscope generated 2-D photograph of a top down images of 8,9, and 10 m trenches after the cure step at the exposure dose of 327mJ/cm². FIG. 4 shows the laser microscope generated 3-D photograph of 15μm square shaped via array at the exposure dose of 327 mJ/cm². Similarhigh resolution photographs were also obtained for 2, 3, and 4 μmtrenches at the exposure dose of 327 mJ/cm², demonstrating that thecompositions are suitable for such fine line lithographic resolutions.

Example 27

The composition of Example 17 was spin coated at a spin speed of 900 rpmfor 30 seconds on 5-inch bare silicon wafers and post apply baked (PAB)at 105-110° C. on a hot plate for 3 minutes. The films were then exposedusing a patterned mask to a broad band Hg-vapor light source (at 365 nmusing a band pass filter) at an exposure dose of 1000 mJ/cm². Thedevelopment of these exposed films by 2.4 wt. % TMAH retained rectanglesof 4.5 mm, 6.5 mm and 15 mm film strips on the wafers. These films werehard baked at 200° C. for 2 hrs in an oven kept under nitrogenatmosphere. The film strips were lifted out of the wafer by immersing in1 wt. % hydrogen fluoride solution and allowed to dry in air. Theserectangular films were cut into 20 mm length and mechanical propertieswere measured by Instron, thermomechanical analysis (TMA) after a stressrelief bake of 10° C. to 250° C. at 5° C./min temperature ramp followedby cooling to 10° C., dynamic mechanical analysis (DMA) without a stressrelief bake and thermogravimetric analysis (TGA) in nitrogen atmosphere.The results are summarized in Table 3.

TABLE 3 Tensile Tensile T_(α) T_(g) T_(d5) Modulus Strength ETB CTE (°C.) (° C.) (° C.) (GPa) (MPa) (%) (ppmK⁻¹) (TMA) (DMA) (TGA) 2.3 ± 0.685 ± 22 17 ± 11 57 315 318 338

Example 28

This Example 28 demonstrates that excellent photoimagable patterns canbe obtained from the compositions of this invention with almost no darkfield loss (DFL) of the film.

The composition of Example 22 was spin coated at a spin speed of 700 rpmfor 30 seconds on a 4-inch thermal oxide silicon wafer. The coated filmwas post apply baked (PAB) at 110° C. on a hot plate for 3 minutes toobtain a film thickness of 10.8 μm. The film was then exposed using acombination of a patterned mask and a variable density mask to a broadband Hg-vapor light source (at 365 nm using a band pass filter). Thefilm was developed for 158 seconds with 2.4 wt. % TMAH in a puddle,rinsed with distilled water and dried using a stream of nitrogen. Apositive tone image was formed and observed under an optical microscope.Both trenches and contact holes were formed in 15 μm resolution. Thefilm thicknesses (FT) in the unexposed area after development was 10.9μm. The unexposed film thickness loss or dark field loss (DFL) of 0% wascalculated based on film thicknesses before and after development. Thefilm was cured at 200° C. for 2 hours in an oven under nitrogenatmosphere. FIG. 5 shows the optical microscope generated 2-D photographof a top down images of trenches and contact holes at 5-100 μm after thecure step at the exposure dose of 791 mJ/cm². The trenches and contactholes are formed at 15 μm resolution.

Comparative Example 7

This Comparative Example 7 demonstrates that it is difficult to obtainphotoimagable compositions from ROMA polymers derived from NBD and MA inwhich MA is ring opened with methanol alone under similar conditions asused to obtain photoimagable compositions of the invention as describedspecifically in Example 27.

The composition of Comparative Example 6 was spin coated at a spin speedof 600 rpm for 30 seconds on a 4-inch thermal oxide silicon wafer. Thecoated film was post apply baked (PAB) at 110° C. on a hot plate for 3minutes to obtain a film thickness of 11 μm. The film was then exposedusing a combination of a patterned mask and a variable density mask to abroad band Hg-vapor light source (at 365 nm using a band pass filter).The film was developed for 6 seconds with 2.4 wt. % TMAH in a puddle,rinsed with distilled water and dried using a stream of nitrogen. Thefilm was completely removed by the development step (film thickness (FT)after development was 0 μm. The unexposed film thickness loss or darkfield loss (DFL) of 100% was calculated based on film thicknesses beforeand after development. The dissolution of both exposed and unexposedareas of the film are too high to generate an image.

Example 29

This Example 29 further illustrates improved properties of thecomposition of this invention, such as for example, shelf lifestability, and improved thermomechanical properties of the post exposurecured films.

The polymer of Example 13 was dissolved in PGMEA to form a 30 wt. %solution. This solution was heated while stirring in a closed reactionvessel under nitrogen atmosphere at 110° C. for 3 hours. A compositionin accordance with this invention was then prepared using this polymersolution having the specific amounts of additives, expressed as partsper hundred resin (phr): TrisP3M6C-2-201 (35 phr) as a photo-activecompound, VG3101L (30 phr) and GE-36 (30 phr) as epoxide crosslinkers,KBM-403E (5 phr) as an adhesion promoter, WPBG-174 (5 phr) as a thermalbase catalyst, FC-4432 (0.3 phr) as a surface leveling agent and PGMEA(260 phr) as the solvent were mixed in an appropriately sized amber HDPEbottle. The mixture was rolled for 18 hours to produce a homogeneoussolution. Particle contamination was removed by filtering the polymersolution consequently through 1 μm, 0.45 μm and 0.20 μm porepolytetrafluoroethylene (PTFE) disc filter, the filtered polymersolution was collected in a low particle HDPE amber bottle and parts ofthe resulting solution stored each at 5° C. and at ambient temperature.

Shelf Life Studies

The viscosity of the composition from Example 29 was monitored for 26days at room temperature. The viscosity changed as follows; day-0, 350cps; day-5, 363 cps; day-7, 356 cps; day-15, 363 cps; day-22, 362 cps;day-26, 412 cps. According to these results the viscosity of thecomposition kept at room temperature increased only about 3% in threeweeks, thus demonstrating that the composition of this invention isstable at room temperature.

Photo Imaging Studies

The composition of Example 29 was spin coated at a spin speed of 500 rpmfor 10 seconds followed by 850 rpm for 30 seconds on a 4-inch thermaloxide silicon wafer. The coated film was post apply baked (PAB) at 105°C. on a hot plate for 3 minutes to obtain a film thickness of 11.22 μm.The film was then exposed using a combination of a patterned mask and avariable density mask to a broad band Hg-vapor light source (at 365 nmusing a band pass filter). The film was developed for 21 seconds with2.4 wt. % TMAH in a puddle, rinsed with distilled water and dried usinga stream of nitrogen. The film thicknesses (FT) after development was9.75 μm. Contact holes and trenches were formed at 5 μm resolution andobserved by an optical microscope. The unexposed film thickness loss ordark field loss (DFL) of 13% was calculated based on film thicknessesbefore and after development. The film was cured at 200° C. for 2 hoursin an oven under nitrogen atmosphere. The film thickness of theunexposed areas lost further 12% and the features generated by photoimaging remained intact at 5 μm resolution as observed by an opticalmicroscope demonstrating that the compositions are suitable for suchfine line lithographic resolutions.

Thermomechanical Properties

The composition of Example 29 was spin coated at a spin speed of 500 rpmfor 10 seconds followed by 900 rpm for 30 seconds on 5-inch bare siliconwafers and post apply baked (PAB) at 105-110° C. on a hot plate for 3minutes. This process was repeated to generate five coated films. Thefilms were then exposed using a patterned mask to a broad band Hg-vaporlight source (at 365 nm using a band pass filter) at an exposure dose of500 mJ/cm². The development of these exposed films by 2.4 wt. % TMAH for30 seconds retained rectangles of 4.5 mm and 6.5 mm strips on thewafers. These films were hard baked at 200° C. for 2 hrs in an oven keptunder nitrogen atmosphere. The film strips were lifted out of the waferby immersing in 1 wt. % hydrogen fluoride solution and allowed to dry inair. These rectangular films were cut into 20 mm length and mechanicalproperties were measured by Instron, thermomechanical analysis (TMA) andthermogravimetric analysis (TGA) in nitrogen atmosphere. The results aresummarized in Table 4.

TABLE 4 Tensile Tensile T_(α) T_(β) T_(d5) Modulus Strength ETB CTE (°C.) (° C.) (° C.) (GPa) (MPa) (%) (ppmK⁻¹) (TMA) (TMA) (TGA) 2.4 ± 0.177 ± 4 36 ± 20 64 328 223 328

It is evident from the data summarized in Table 4 the composition ofthis invention exhibit excellent thermomechanical properties. T_(α) andT_(β) are respectively primary and secondary glass transitiontemperatures (T_(g)) observed as measured by TMA. T_(d5) is the measureof temperature at which 5 percent weight loss of the composition wasobserved as measured by TGA.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition comprising: a polymer comprisingone or more distinct first repeating unit represented by formula (IA),each of said first repeating unit is derived from a monomer of formula(I):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit; each of R₁, R₂, R₃ and R₄ is independently selected fromthe group consisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,—CO₂R, halogen and a group of formula (A):

where R is (C₁-C₆)alkyl or tri((C₁-C₆)alkyl)silyl; and R_(a) is selectedfrom the group consisting of —(CH₂)_(p)—, —(CH₂)_(q)—OCH₂— and—(CH₂)_(q)—(OCH₂CH₂)_(r)—OCH₂—, where p is an integer from 0 to 6, q isan integer from 0 to 4 and r is an integer from 0 to 3; one or moredistinct second repeating unit represented by formula (IIA), said secondrepeating unit is derived from a monomer of formula (II):

wherein: each of R₅ and R₆ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₉)alkyl and fluorinatedor perfluorinated(C₁-C₉)alkyl; R₇ is selected from the group consistingof hydrogen, linear or branched (C₁-C₉)alkyl, fluorinated orperfluorinated(C₁-C₉)alkyl, and—(CH₂)_(a)-(0-(CH₂)_(b))_(c)—O(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4; and one or more distinct third repeating unitrepresented by formula (IIIA), said third repeating unit is derived froma monomer of formula (III):

wherein: each of R₈ and R₉ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₉)alkyl and fluorinatedor perfluorinated(C₁-C₉)alkyl; R₁₀ is selected from the group consistingof hydrogen, linear or branched (C₁-C₁₆)alkyl, (C₃-C₉)cycloalkyl,(C₃-C₉)cycloalkyl(C₁-C₁₀)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₄)alkyl,(C₁-C₁₆)alkylCO₂R, (C₁-C₁₆)alkylCH₂OR, (C₆-C₁₀)arylCO₂R and(C₆-C₁₀)arylCH₂OR; where R is hydrogen, (C₁-C₆)alkyl ortri((C₁-C₆)alkyl)silyl; and wherein molar amount of repeating unit offormula (IIIA) is at least 3 mole percent; a photoactive compound; across-linking agent; and a carrier solvent.
 2. The composition accordingto claim 1, wherein said polymer further comprises one or more distinctfourth repeat unit of formula (IVA) derived from a monomer of formula(IV):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit; m is an integer 0, 1 or 2; each of R₁₁, R₁₂, R₁₃ and R₁₄ isindependently selected from the group consisting of hydrogen, linear orbranched (C₁-C₁₆)alkyl, hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₅-C₁₀)heteroaryl,(C₅-C₁₀)heteroaryl(C₁-C₃)alkyl, hydroxy, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,—(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₄)alkyl, where a, b and c areintegers from 1 to 4, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl, (C₆-C₁₀)aryloxy,(C₅-C₁₀)heteroaryloxy, (C₁-C₆)acyloxy and halogen.
 3. The compositionaccording to claim 1, wherein said polymer further comprises a repeatunit of formula (IB) derived from the monomer of formula (I):

wherein R₁, R₂, R₃ and R₄ are each as defined in claim
 1. 4. Thecomposition according to claim 1, wherein said polymer comprises one ormore distinct repeating units of formula (IA) wherein, each of R₁, R₂,R₃ and R₄ is independently selected from the group consisting ofhydrogen, methyl, ethyl, linear or branched (C₁-C₁₂)alkyl andphenyl(C₁-C₃)alkyl.
 5. The composition according to claim 1, whereinsaid polymer comprises one or more distinct repeating units of formula(IIA) wherein, R₅ and R₆ are the same or different and independently ofeach other selected from hydrogen or methyl; and R₇ is selected fromhydrogen, methyl, ethyl, n-propyl, iso-propyl or n-butyl.
 6. Thecomposition according to claim 1, wherein said polymer comprises one ormore distinct repeating units of formula (IIIA) wherein, R₈ and R₉ arethe same or different and independently of each other selected fromhydrogen or methyl; and R₁₀ is selected from hydrogen, methyl, ethyl,n-propyl, iso-propyl, n-butyl, cyclopentyl, cyclohexyl, cycloheptyl,phenyl, benzyl or phenethyl.
 7. The composition according to claim 2,wherein said polymer comprises one or more distinct repeating units offormula (IVA) wherein: m is 0; each of R₁₁, R₁₂, R₁₃ and R₁₄ isindependently selected from the group consisting of hydrogen, methyl,ethyl, linear or branched (C₁-C₁₂)alkyl, phenyl(C₁-C₃)alkyl and—(CH₂)_(a)—(O—(CH₂)_(b))_(c)—O—(C₁-C₄)alkyl, where a is 1 or 2, b is 2to 4 and c is 2 or
 3. 8. The composition according to claim 1, whereinsaid polymer is having one or more distinct first repeating unit derivedfrom a respective monomer selected from the group consisting of:bicyclo[2.2.1]hepta-2,5-diene (norbornadiene);2-methylbicyclo[2.2.1]hepta-2,5-diene;2-butylbicyclo[2.2.1]hepta-2,5-diene;2-hexylbicyclo[2.2.1]hepta-2,5-diene;2-octylbicyclo[2.2.1]hepta-2,5-diene;2-phenethylbicyclo[2.2.1]hepta-2,5-diene; tert-butylbicyclo[2.2.1]hepta-2,5-diene-2-carboxylate; trimethylsilylbicyclo[2.2.1]hepta-2,5-diene-2-carboxylate; andbicyclo[2.2.1]hepta-2,5-dien-2-ylmethanol.
 9. The composition accordingto claim 1, wherein said polymer is having one or more distinct secondrepeating unit derived from a respective monomer selected from the groupconsisting of: maleic anhydride; 2-methyl-maleic anhydride(3-methylfuran-2,5-dione); 2,3-dimethyl-maleic anhydride(3,4-dimethylfuran-2,5-dione); 2-ethyl-maleic anhydride(3-ethylfuran-2,5-dione); 2,3-diethyl-maleic anhydride(3,4-diethylfuran-2,5-dione); 2-trifluoromethyl-maleic anhydride(3-trifluoromethylfuran-2,5-dione); 2,3-bis(trifluoromethyl)-maleicanhydride (3,4-bis(trifluoromethyl)furan-2,5-dione); and2-methyl-3-trifluoromethyl-maleic anhydride(3-methyl-4-(trifluoromethyl)furan-2,5-dione).
 10. The compositionaccording to claim 1, wherein said polymer is having one or moredistinct third repeating unit derived from a respective monomer selectedfrom the group consisting of: maleimide; N-methylmaleimide;N-butylmaleimide; 3-methylmaleimide (3-methylpyrrolidine-2,5-dione);N-cyclohexylmaleimide; N-phenylmaleimide; N-benzylmaleimide; andN-phenethylmaleimide.
 11. The composition according to claim 2, whereinsaid polymer is having one or more distinct fourth repeating unitderived from a respective monomer selected from the group consisting of:norbornene; 5-hexylbicyclo[2.2.1]hept-2-ene;5-octylbicyclo[2.2.1]hept-2-ene; 5-decylbicyclo[2.2.1]hept-2-ene;5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON);1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecane;5-benzylbicyclo[2.2.1]hept-2-ene; and5-phenethylbicyclo[2.2.1]kept-2-ene.
 12. The composition according toclaim 1, wherein said polymer is selected from the group consisting of:a terpolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol andN-phenylmaleimide; a terpolymer of norbornadiene (NBD), maleic anhydridein which maleic anhydride repeating unit is ring opened with methanoland maleimide; a terpolymer of norbornadiene (NBD), maleic anhydride inwhich maleic anhydride repeating unit is ring opened with methanol andN-cyclohexyl-maleimide; a tetrapolymer of norbornadiene (NBD),5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON),maleic anhydride in which maleic anhydride repeating unit is ring openedwith methanol and N-phenylmaleimide; a tetrapolymer of norbornadiene(NBD), maleic anhydride in which maleic anhydride repeating unit is ringopened with methanol, N-cyclohexylmaleimide and maleimide; and atetrapolymer of norbornadiene (NBD), maleic anhydride in which maleicanhydride repeating unit is ring opened with methanol, N-phenylmaleimideand maleimide.
 13. The composition according to claim 1, wherein saidphotoactive compound comprises one or more of a1,2-naphthoquinonediazide-5-sulfonyl moiety,1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structuralformulae (Va) and (Vb), respectively:

or a sulfonyl benzoquinone diazide group represented by structuralformula (Vc):


14. The composition according to claim 13, wherein said photoactivecompound is selected from the group consisting of:

wherein at least one of Q is a group of formula (Va) or (Vb):

and the remaining Q is hydrogen.
 15. The composition according to claim1, wherein said cross-linking agent is selected from the groupconsisting of:

and a mixture in any combination thereof.
 16. The composition accordingto claim 1, wherein said solvent is selected from the group consistingof propyleneglycol monomethylether acetate (PGMEA), N-methylpyrrolidone(NMP) and γ-butyrolactone (GBL) and a mixture in any combinationthereof.
 17. The composition according to claim 1, wherein saidcomposition further comprises one or more additives selected from thegroup consisting of: a photo base generator; a thermal base generator;adhesion promoters; antioxidants; surfactants; and mixtures in anycombination thereof.
 18. A process for forming a cured product,comprising: (i) applying the layer forming polymer composition of claim1 on a substrate to form a coating film, (ii) exposing the coating filmto light through a desired pattern mask, (iii) dissolving and removingthe exposed portions by developing with an alkaline developer to obtainthe desired pattern, and (iv) heating the obtained desired pattern. 19.A cured product obtained by curing the composition of claim
 1. 20. Apolymer comprising one or more distinct first repeating unit representedby formula (IA), each of said first repeating unit is derived from amonomer of formula (I):

wherein:

represents a position at which the bonding takes place with anotherrepeat unit; each of R₁, R₂, R₃ and R₄ is independently selected fromthe group consisting of hydrogen, linear or branched (C₁-C₁₆)alkyl,hydroxy(C₁-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,—CO₂R, halogen and a group of the formula (A):

where R is (C₁-C₆)alkyl or tri((C₁-C₆)alkyl)silyl; and R_(a) is selectedfrom the group consisting of —(CH₂)_(p)—, —(CH₂)_(q)—OCH₂— and—(CH₂)_(q)—(OCH₂CH₂)_(r)—OCH₂—, where p is an integer from 0 to 6, q isan integer from 0 to 4 and r is an integer from 0 to 3; one or moredistinct second repeating unit represented by formula (IIA), said secondrepeating unit is derived from a monomer of formula (II):

wherein: each of R₅ and R₆ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₉)alkyl and fluorinatedor perfluorinated(C₁-C₉)alkyl; R₇ is selected from the group consistingof hydrogen, linear or branched (C₁-C₉)alkyl, fluorinated orperfluorinated(C₁-C₉)alkyl, and—(CH₂)_(a)-(0-(CH₂)_(b))_(c)—O—(C₁-C₆)alkyl, where a, b and c areintegers from 1 to 4; and one or more distinct third repeating unitrepresented by formula (IIIA), said third repeating unit is derived froma monomer of formula (III):

wherein: each of R₈ and R₉ is independently selected from the groupconsisting of hydrogen, linear or branched (C₁-C₉)alkyl and fluorinatedor perfluorinated(C₁-C₉)alkyl; R₁₀ is selected from the group consistingof hydrogen, linear or branched (C₁-C₁₆)alkyl, (C₃-C₉)cycloalkyl,(C₃-C₉)cycloalkyl(C₁-C₁₀)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₄)alkyl,(C₁-C₁₆)alkylCO₂R, (C₁-C₁₆)alkylCH₂OR, (C₆-C₁₀)arylCO₂R and(C₆-C₁₀)arylCH₂OR; where R is hydrogen, (C₁-C₆)alkyl ortri((C₁-C₆)alkyl)silyl; and wherein molar amount of repeating unit offormula (IIIA) is at least 3 mole percent.